Patent Application
20200277496
The present invention relates to the field of asphalt binders having a low bitumen content, and methods for preparing said. These asphalt binders are useful for preparing asphalt compositions, e.g. for asphalt road construction, in particular stone mastic asphalt or porous asphalt road construction.
Asphalt is generally prepared by mixing aggregate and filler materials by a bitumen based binder.
Bitumen is derived from the heaviest portion from the oil distillation process. It may have different properties due to the different origins of the oil as well as due to the different distillation processes employed. However, bitumen can be characterized by the presence of four classes of substances each having different molecular weight ranges: saturates, aromatics, resins, and asphaltenes.
Since bitumen is obtained from fossil sources, there is a desire to (partly) replace bitumen by alternatives with a higher sustainability in terms of decreased CO2-emission and favourable environmental impact.
Lignin from biomass is known as a potential substitute for part of the bitumen in asphalt and other applications. Lignin acts in plants as a binder to provide strength and rigidity to the plants and has structural similarities to the aromatic and asphaltene fractions of bitumen, for example in that both contain similar unsaturated aromatic rings joined by alkyl chains. Furthermore, lignin also has adhesive and UV stability properties.
Lignin is one of the most abundant natural polymers (next to cellulose and hemi cellulose) present in plant material. It is generated as a side stream in the production process for pulp and paper and as a non-fermentable side stream in the production of cellulosic bioethanol.
For the above reasons, asphalt binder compositions have already been described which contain bitumen and lignin. However, processing of the asphalt compositions that are obtained with such binder compositions requires high temperatures. Furthermore, the obtained asphalt has a limited strength.
Therefore, it is an objective of the present invention to overcome one or more disadvantages as described above, and particularly to provide for an improved asphalt binder.
The present disclosure provides for a composition comprising
The composition may be an asphalt binder composition or asphalt composition. Accordingly, the present disclosure also relates to a paving or roofing comprising the composition of the disclosure. Further, the present disclosure relates to a method of preparing an asphalt composition, comprising mixing bitumen with filler material, adding lignin preparation and vegetable oil to the mixture obtained, preferably wherein the lignin preparation and the vegetable oil are added (substantially) simultaneously.
The technology of the present disclosure leads to the partial, but significant, substitution of bitumen, a fossil derived distillation fraction of crude oil. The present disclosure will therefore allow for a significantly lower use of fossil bitumen, and will increase independency of the fossil industry and will save energy and improve CO2 footprint of the manufacturing process for asphalt.
In the present disclosure, a specific lignin preparation is used in combination with a (boiled) vegetable oil or derivative thereof to substitute preferably more than 50% of the bitumen in asphalt binders. It has been found that a lignin preparation with the specific characteristics according to the present disclosure provides for an improved asphalt strength, both under dry and wet conditions.
The lignin is preferably applied without prior modification and typically in a 50% substitution level to bitumen. Addition of the vegetable oil is beneficial to reach improved compatibility (e.g. better mixing) and lower processing temperatures at which no observable crosslinking occurs.
In a first aspect, the present disclosure relates to a composition comprising
The composition can be used as or comprised in an asphalt (binder) composition. Accordingly, the present disclosure further relates to a paving comprising the composition as described herein, as well as a roofing comprising the composition as described herein.
As mentioned, a first preferred ingredient of the composition is bitumen, which is known for different applications, the most important being as aggregate blend for road paving. Bitumen is derived from the heaviest portion from the oil distillation process. It may have different properties due to the different origins of the oil as well as due to the different distillation processes employed. However, bitumen can be characterized by the presence of four classes of substances each having different molecular weight ranges: saturates, aromatics, resins, and asphaltenes. The bitumen in the present composition may be selected from virgin bitumen, recycled bitumen, or mixtures thereof. The bitumen may be present in an amount of at least 0, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100 wt. % and/or at most 300, 250, 200, 180, 150, 125, 110 wt. %, preferably 80-120 wt. % with respect to the weight of the lignin preparation.
The composition further comprises (boiled) vegetable oil, or non-fossil derived oil, preferably chosen from linseed oil, soybean oil, sunflower oil, and safflower oil. Preferably, the vegetable oil has a dynamic viscosity of 0.01-1600 Pa·s at 20° C. or 0.01-1000, 0.03-500, or 0.05-250, preferably 0.1-100, 0.2-50, 0.3-20, 0.4-10, 0.5-5 or 0.5-2 Pa·s at 20° C. Kinematic viscosity may be determined by using an Ubbelohde viscometer according to ASTM D 445 or its equivalent BS 188. The dynamic viscosity can be calculated from the kinematic viscosity data by multiplying the latter by the density (see e.g. Gallagher et al; Am. Oil. Chem. Soc., 54, 68-70, 1977).
A higher dynamic viscosity of the vegetable oil can be achieved through boiling, thereby obtaining a boiled vegetable oil with increased viscosity as compared to vegetable oil that has not been boiled. Here, boiling may refer to oxidative polymerization of the vegetable oil so as to obtain the desired dynamic viscosity. Boiled linseed oil is sometimes referred to as lynpave oil.
The vegetable oil may be a derivative of a natural vegetable oil (preferably non-fossil based) such as a polyol ester thereof or vegetable oil based alkyd. Such alkyds are typically prepared by reacting a vegetable oil or fatty acid, with polyhydric alcohols like (di)pentaerythritol, glycerol, sorbitol, xylitol and the like, and a di- or triacid (anhydride); e.g. succinic acid, furandicarboxylic acid or phthalic acid (anhydride). Alternatively and/or additionally, the vegetable oil may be modified. Preferably, the vegetable oil is selected from the group consisting of linseed oil, soybean oil, sunflower oil, and safflower oil, and/or in the most preferred embodiment the vegetable oil is unsaturated.
Alternatively and/or additionally to the above-mentioned derivatives of vegetable oil, a drying fatty acid, semi-drying fatty acid or mixture thereof may be used in the present disclosure as an vegetable oil derivative, such as ethylenically unsaturated conjugated or non-conjugated C12 to C24 carboxylic acids, for example oleic, ricinoleic, linoleic, linolenic, licanoic acid and eleostearic acids or mixture thereof, typically used in the form of mixtures of fatty acids derived from natural or synthetic oils. Examples of suitable natural oils include but are not limited to safflower, tall oil, calendula oil, rapeseed oil, peanut oil, soya bean oil, tung oil, linseed oil, sardine oil, herring oil, sesame oil, olive oil, dehydrated castor oil, tallow oil, sunflower oil, cottonseed oil and mixtures thereof.
The vegetable oil or derivative thereof may be present in at least 0, 0.1, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0 wt. %, and/or at most 10, 9, 8, 7, 5, 4, 3, 2 wt. %, preferably 3-10 wt. %, with respect to the weight of the bitumen.
A third ingredient of the composition is the lignin preparation, preferably in a dried powder form or having a water content of less than 25, 20, 15, 10, or 5 wt. %. Preferably, the lignin preparation is present in at least 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150 wt. % and/or at most 200, 180, 150 wt %, preferably 80-120 wt. % with respect to the weight of the bitumen.
Lignin is one of the most abundant natural polymers (next to cellulose and hemi cellulose) present in plant material. It is generated as a side stream in the production process for pulp and paper and as a non-fermentable side stream in the production of bioethanol.
As mentioned herein before, the lignin preparation according to the present disclosure has a specified purity and/or a lower impurity content, e.g. a lower content in carbohydrates, proteins, and/or ash. It was particularly found that a higher purity of the lignin preparation leads to an improved binding capacity of the lignin preparation, and accordingly, when applied in an asphalt (binder) composition, an improved asphalt strength, both under dry and wet conditions. Without being bound by any theory, it appears that the presence of too much impurities, such as carbohydrates, proteins, and/or ash, impedes the binding function of the lignin preparation.
The lignin purity and/or the impurity content may for example be determined by a two-step sulfuric acid hydrolysis of the lignin preparation starting with 12 M H2SO4 at 30° C. for 1 h followed by 1 M H2SO4 at 100° C. for 3 h. The hydrolysate can then be neutralized by calcium carbonate until acidic pH as indicated by bromophenol blue. Resulting monosaccharides are separated and quantified for example by HPAEC-PAD on a Dionex CarboPac PA1 column and precolumn, preferably under the following conditions: sodium hydroxide/water gradient at 35° C.; flow rate 1 ml min-1. Postcolumn addition of 500 mM NaOH at a flow rate of 0.2 ml min-1 may be used for detection. Ash in lignin can be determined after complete combustion at 800° C. during 4-8 h. Methods were derived from TAPPI standards.
Further, the lignin has a preferred average molecular weight. Average molecular weight of the lignin may be determined as follows. Lignin samples of 1 mg/ml may be dissolved in 0.5 M NaOH and can be injected into TSKgel guardcolumn PWxl, preferably with Column Size: 6.0 mmI.D.×4 cm, Particle Size: 12 um and two serial connected TSKgel GMPWxl, Column Size: 7.8 mmI.D.×30 cm, Particle Size: 13 um. Samples can then be eluted with the same solvent. Preferred conditions: flow 1 ml min-1, column temperature 25° C., and detection at 280 nm. Standards for calibration of the molar mass distribution: sodiumpolystyrene sulfonates (Mw range: 891 to 976 000 Da) and phenol.
The lignin preparation may be further characterized by
Softening temperature may for example be determined as follows. 20 mg of dried lignin may be put in hermetically closed stainless steel cups. In a DSC Pyris Perkin Elmer, the samples can be heated from −40° C. to 190° C. with 10° C./min. After annealing with 100° C./min to −40° C., the samples can be heated to 190° C. with 10° C./min. The Tg can then be measured from the second heating thermogram.
Furthermore, the phenolic and aliphatic hydroxyl group content can be measured as follows. In a 1-ml vial, 30 mg of lignin was mixed with 100 ml N,N-Dimethylformamide (DMF)/pyridine (1:1 v/v) and 100 ml internal standard solution containing 15 mg ml-1 cyclohexanol (internal standard) and 2.5 mg ml-1 chromium(III) acetylacetonate in pyridine. This suspension can then be stirred for 4-16 h at room temperature. Derivatization (100 ml) reagent (2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphopholane) may then be mixed with 400 ml of CDCl3 prior to addition to the lignin suspension. After mixing, the mixture can be analyzed by NMR (Bruker 400 MHz), preferably with 308 pulse angle, inverse gated proton decoupling, a delay time of 5 s and 256 scans. Signal assignment was performed as described by Granata and Argyropoulos (Magnetic resonance in chemistry, vol. 33, 375-382, 1995).
Preferably one or more of the following lignin preparations is used: Soda mixed straw/Sarkanda grass (P1000); Kraft softwood (Indulin AT); Hydrolysis poplar obtainable from sources as described in the Example.
In a preferred embodiment, the composition according to the present disclosure is a binder for preparing asphalt, i.e. an asphalt binder, preferably comprising
In another preferred embodiment, the composition according to the present disclosure is an asphalt composition, such as a stone mastic asphalt composition or a porous asphalt (or open graded asphalt) composition, preferably comprising
Such asphalt composition preferably has a consistency as measured by a penetration of between 10-350 10−1 mm at 25° C. according to ASTM D5.
In a further aspect, the present disclosure relates to a method of preparing an asphalt composition, preferably an asphalt composition as described above, comprising
(a) mixing bitumen with filler material, wherein the filler material preferably comprises stones, sand, and/or rubble;
(b) adding lignin preparation and vegetable oil to the mixture obtained in step (a), wherein the lignin preparation and the vegetable oil are added in separate steps or as a premixture, or preferably wherein the lignin preparation and the vegetable oil are added substantially simultaneously (such as within 0.25, 0.5, 1, or 2 hours).
Step (a) is preferably performed at a temperature of 90-180, 100-150° C., or 110-140, preferably 120-140° C.
It will be evident that the present disclosure further provides for the use of the lignin preparation as described herein for improving asphalt strength.
In this document and in its claims, the verb “to comprise” and its conjugations is used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. In addition, reference to an element by the indefinite article “a” or “an” does not exclude the possibility that more than one of the element is present, unless the context clearly requires that there be one and only one of the elements. The indefinite article “a” or “an” thus usually means “at least one”.
1. Composition comprising
2. Composition according to item 1, wherein the lignin preparation is further characterized by
3. Composition according to any one of the previous items, wherein the vegetable oil is present in at least 0.5, or 1 wt. %, preferably 1-10 wt. %, with respect to the weight of the bitumen.
4. Composition according to any one of the previous items, wherein the lignin preparation is present in at least 10, 25, or 50 wt. %, preferably 80-120 wt. % with respect to the weight of the bitumen.
5. Composition according to any one of the previous items, wherein the vegetable oil is chosen from linseed oil, soybean oil, sunflower oil, and safflower oil; and/or wherein the vegetable oil has a dynamic viscosity of 0.1-1600 Pa·s at 20° C., preferably 0.1-100 Pa·s at 20° C.
6. Composition according to any one of the previous items, wherein the bitumen is selected from virgin bitumen, recycled bitumen, or mixtures thereof.
7. Composition according to any one of the previous items, wherein the composition is a binder for preparing asphalt, preferably comprising
8. Composition according to any one of items 1-6, wherein the composition is an asphalt composition, preferably comprising
9. Composition according to item 8, wherein the composition has a consistency as measured by a penetration of between 10-350 10−1 mm at 25° C. according to ASTM D5.
10. Paving comprising the composition according to any one of previous items.
11. Roofing comprising the composition according to any one of the previous items.
12. Method of preparing an asphalt composition according to item 8, comprising
(a) mixing bitumen with filler material, wherein the filler material preferably comprises stones, sand, and/or rubble;
(b) adding lignin preparation and vegetable oil to the mixture obtained in step (a), wherein the lignin preparation and the vegetable oil are added in separate steps or as a premixture, or preferably wherein the lignin preparation and the vegetable oil are added substantially simultaneously.
13. Method according to item 12, wherein step (a) is performed at a temperature of 100-150° C., preferably 120-140° C.
14. Use of a lignin preparation for improving asphalt strength, wherein the lignin preparation is characterized by
15. Use according to item 14, wherein the lignin preparation is as defined in item 2.
Lignin Types
Soda Mixed Straw/Sarkanda Grass (P1000)
Starting material: the mill feedstock is close to 100% wheat straw for soda pulping for production of cellulose pulp in India.
Process description: the mill uses soda pulping in a continuous digester used for the production of bleachable non-wood pulp that goes into printing and writing papers. Lignin is solubilized in black liquor. This lignin was isolated by an LPS process (lignin precipitation process) as described by Abaecherli et al. 2000. Method for preparing alkaline solutions containing aromatic polymers (EP 0970275 B1). Said document relates to a process for the preparation of by acidification precipitable aromatic polymers alkaline solutions, which allows the separation of these polymers in solid form and drying in air at normal pressure and employing temperatures of between 40° and 110° C. without blackening.
Product Description: Protobind™ 1000 (P1000) is a high purity natural polyphenolic material (soda lignin) specially formulated for use as a partial replacement of phenol in phenolic resin industries. This product is now being industrially produced in India in dry powder form using state-of-the-art Swiss technology (EP 0970275 B1). With access to an annual production capacity of more than 10,000 metric tons. Obtainable for example from GreenValue Enterprises LLC.
Pulping is operated by Kuantum Papers and lignin recovery (using GreenValue's technology) is operated by Greencone Environs.
Kraft Softwood (Indulin AT)
Starting material: Softwood pine
Description of pulp process: the kraft process (also known as kraft pulping or sulfate process) is a process for conversion of wood into wood pulp, which consists of almost pure cellulose fibers, the main component of paper. The kraft process entails treatment of wood chips with a hot mixture of water, sodium hydroxide, and sodium sulfide, known as white liquor, that breaks the bonds that link lignin, hemicellulose, and cellulose. The technology entails both mechanical and chemical steps. The lignin is isolated from black liquor by precipitation and further purified.
Product description: purified kraft softwood lignin: Indulin AT. Obtainable from for example Ingevity Holdings SPRL, Belgium. Production is at Ingevity Chemical.
Hydrolysis Straw Lignin Produced by DONG Energy/Inbicon.
Wheat straw was processed via technology available from Inbicon. This process uses a hydrothermal pretreatment to open up the cellulosic fibres for following hydrolysis and fermentation to produce cellulosic ethanol (Inbicon patent disclosures). The lignin-rich non-fermentable stream was isolated and dried for asphalt application (see e.g. Le, D. M., Frosch Mogensbaek, bitumen compositions comprising lignin, WO 2017/088892 A1). Two hydrolysis straw lignins have been tested. These differ according to different processing steps to produce a regular lignin land a more purified lignin 2.
Hydrolysis Poplar
Poplar wood was treated by a modified steam explosion process to open up the lignocellulosic fibres for subsequent hydrolysis and fermentation to produce cellulosic ethanol. The lignin-rich non-fermentable stream was isolated and dried for asphalt application.
Methods of Analysis (I)
(also described by Gosselink et al 2010, Holzforschung 64(1) 2010, 193-200)
Measuring Purity and Impurity Content
Lignin was hydrolyzed by a two-step sulfuric acid hydrolysis starting with 12 M H2SO4 at 30° C. for 1 h followed by 1 M H2SO4 at 100° C. for 3 h. The hydrolysate was neutralized by calcium carbonate until acidic pH as indicated by bromophenol blue. Resulting monosaccharides were separated and quantified by HPAEC-PAD on a Dionex CarboPac PA1 column and precolumn under the following conditions: sodium hydroxide/water gradient at 35° C.; flow rate 1 ml min-1. Postcolumn addition of 500 mM NaOH at a flow rate of 0.2 ml min-1 was used for detection. Ash in lignin was determined after complete combustion at 800° C. during 4-8 h.
Methods were Derived from TAPPI Standards.
Measuring Molecular Weight Range
Lignin samples of 1 mg/ml dissolved in 0.5 M NaOH were injected into TSKgel guardcolumn PWxl, Column Size: 6.0 mmI.D.×4 cm, Particle Size: 12 um and two serial connected TSKgel GMPWxl, Column Size: 7.8 mmI.D.×30 cm, Particle Size: 13 um. Samples were eluted with the same solvent. Conditions: flow 1 ml min-1, column temperature 25° C., and detection at 280 nm. Standards for calibration of the molar mass distribution: sodiumpolystyrene sulfonates (Mw range: 891 to 976 000 Da) and phenol.
Measuring Softening Temperature
20 mg of dried lignin was put in hermetically closed stainless steel cups. In a DSC Pyris Perkin Elmer, the samples were heated from −40° C. to 190° C. with 10° C./min. After annealing with 100° C./min to −40° C., the samples were heated to 190° C. with 10° C./min. The Tg was measured from the second heating thermogram.
Measuring Phenolic and Aliphatic Hydroxyl Groups
In a 1-ml vial, 30 mg of lignin was mixed with 100 ml N,N-Dimethylformamide (DMF)/pyridine (1:1 v/v) and 100 ml internal standard solution containing 15 mg ml-1 cyclohexanol (internal standard) and 2.5 mg ml-1 chromium(III) acetylacetonate in pyridine. This suspension was stirred for 4-16 h at room temperature. Derivatization (100 ml) reagent (2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphopholane) was mixed with 400 ml of CDCl3 prior to addition to the lignin suspension. After mixing, the mixture was analyzed by NMR (Bruker 400 MHz), with 308 pulse angle, inverse gated proton decoupling, a delay time of 5 s and 256 scans. Signal assignment was performed as described by Granata and Argyropoulos (J. Agric. Food Chem. 43:1538-1544, 1995; Magnetic resonance in chemistry, vol. 33, 375-382, 1995).
Measuring Dry Strength and Wet Strength
Dry strength and wet strength were measured as described in Hossain, M. I., and Tarefder, R. A., (2013), Effects of Moisture in Asphalt Concrete, Basic Research Journal of Engineering Innovation, 1(1), pp 16-25.
Methods of Analysis (2)
Measuring the Acoustic Properties of Road Surfaces
For the measurement of the rolling noise level of vehicles on various road surface types, two measurement methods have been developed within the International Organization for Standardization (ISO). This concerns the:
[1]
The CPX method consists of a system where the noise of a set of tires is measured at a short distance when it rolls over the road surface. This measurement with a ‘noise measurement trailer’ provides insight into the course of the noise level over the entire section length.
The measurements are carried out with two different standard tires. The measuring tire P1 is representative of the noise of light motor vehicles. The result is displayed as CPXP. The second tire is measuring tire H1. The result is displayed as CPXH and is considered to be representative of the noise of heavy motor vehicles.
[2]
In the SPB measurement, the maximum A-weighted noise level and vehicle speed are recorded for individual vehicle passages. The noise level is measured at a fixed distance from the middle of the driving lane to be measured. The measurement is carried out for at least 100 light motor vehicles and, if possible, 50 heavy motor vehicles. The reliability value at which the SPB result is considered to be reliable must be less than or equal to 0.3 dB (A) for light motor vehicles. For heavy motor vehicles this limit value is 0.8 dB (A).
Both methods can be used to determine the acoustic properties of road surfaces. In the present disclosure, both methods were used and the results averaged.
Measuring Rolling Resistance
The rolling resistance is the mechanical energy that is converted into heat when a tire rolls over a certain distance on the road surface. The rolling resistance coefficient is defined as:
RRC=Frr/Fz,
wherein RRC is the rolling resistance coefficient [kg/t], Frr is the force that is necessary to get the vehicle moving in the desired direction [N], and Fz is gravity (N).
In the above formula, the rolling resistance coefficient (RRC) is expressed as a dimensionless unit. Because the RRC is usually between 0.5% and 1.5%, writing it down in whole numbers leads to four zeros after the comma, which can lead to misunderstandings about the order of magnitude. In the literature, the RRC is therefore often given in percent, or kg/ton.
The rolling resistance measurements were carried out with the rolling resistance trailer of the TU Gdansk from Poland.
Measuring Brake Deceleration
This method describes the determination of the braking deceleration value for a homogeneous road section by means of a brake test. In this method, a measuring vehicle is used on a dry road surface with completely blocked wheels in a series of brakes from 80 to 0 km/h. The measuring system consists of a measuring vehicle in which is a braking deceleration meter is mounted which records and stores the braking deceleration during braking. After the measuring vehicle has been brought to a measuring speed of 80 km/h, the brake pedal is pressed fully (emergency stop, no ABS). The brake pedal will not be released before the vehicle has completely stopped.
The requirements for the measuring vehicle are:
The average braking deceleration between the moment of braking and the complete stop of the vehicle can then be calculated.
Characteristics of the Different Lignin Preparation Types
1= Lignin partly soluble in SEC eluent
Method of Preparing Asphalt Binder
For each of the different lignin preparation types, a binder composition was prepared which was tested in Stone Mastic asphalt and in Porous asphalt. Lignin preparation and bitumen were applied in equal amounts in the binder composition. In the case of stone mastic asphalt binder, 1.5 wt. % of lynpave oil (boiled linseed oil), based on total asphalt binder, was applied to allow processing of the stone mastic bio-asphalt at 130° C.
For preparing the stone mastic asphalt compositions, first a hot mixture of stones, sand, filler, and a preparation of bitumen (both at 130° C.) was prepared and mixed, after that the lignin preparation in powder form and the vegetable oil were simultaneously added (at ambient temperature). In this way, a bitumen layer covers the stones, and better mixing with the lignin preparation is achieved. The ratio between stones, sand and filler was chosen such as to provide for a dense SMA premixture. The total mixture was mixed in a drum. The asphalt composition was then densified in a gyrator to the desired test surfaces.
For preparing the porous asphalt composition, first a hot mixture of stones (and sand, filler) and a preparation of bitumen (both at 130° C.) was prepared. The ratio between stones, sand and filler was chosen such as to provide for a water draining porous asphalt premixture. The bitumen preparation, together with a lignin preparation in powder form were added to the hot stones and mixed in a twin shaft Pugmill. It was found that vegetable oil is not required for porous asphalt compositions. Subsequently, the asphalt composition was densified in a gyrator to the desired test surfaces.
Results of Binder Compositions in Stone Mastic Asphalt (I)
Results of Binder Compositions in Stone Mastic Asphalt (2)
Results of Binder Compositions in Porous Asphalt
| Number | Date | Country | Kind |
|---|---|---|---|
| 17201291.6 | Nov 2017 | EP | regional |
This application is the National Stage of International Application No. PCT/EP2018/081097, filed Nov. 13, 2018, which claims the benefit of European Application No. 17201291.6, filed Nov. 13, 2017, the contents of which is incorporated by reference herein.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2018/081097 | 11/13/2018 | WO | 00 |
