Patent Grant
10584442
This application is a 35 U.S.C. 371 national-stage application of PCT/EP2015/076668, filed Nov. 16, 2015, and claims priority under 35 U.S.C. 119 to European Patent Application No. 14193410.9, filed Nov. 17, 2014, and European Patent Application No. 15166103.0, filed May 1, 2015, the contents of which are fully incorporated herein by reference.
This application contains a Sequence Listing in computer readable form. The computer readable form is incorporated herein by reference.
The present invention relates to the removal of hemicelluloses (partly or completely) from paper-grade alkaline pulp (such as kraft pulp or soda pulp) thereby upgrading the pulp e.g. into dissolving-grade pulp using a combination of enzyme treatment, hot caustic extraction and optionally one or more bleaching steps.
Pulp is a lignocellulosic fibrous material prepared by chemically or mechanically separating cellulose fibres from wood, fibre crops or waste paper.
A pulp mill converts wood chips or other plant fibre source into a thick fibre board (market pulp) which can be shipped and traded as paper-grade or dissolving-grade pulp. Pulp can be manufactured using mechanical, semi-chemical or fully chemical methods (e.g. kraft and sulfite processes). The finished product may be either bleached or non-bleached, depending on the customer requirements.
Wood and other plant materials used to make pulp contain three main components (apart from water): cellulose, lignin and hemicelluloses. The aim of pulping is to break down the bulk structure of the fibre source, be it chips, stems or other plant parts, into the constituent fibres. Chemical pulping achieves this by degrading most part of the lignin and to a different extent hemicelluloses into small, water-soluble molecules which can be washed away from the cellulose fibres while controlling the extent of cellulose degradation. The various mechanical pulping methods, such as groundwood (GW) and refiner mechanical pulping (RMP), physically tear the cellulose fibres from each other. Much of the lignin remains adhering to the fibres. There are a number of related hybrid pulping methods that use a combination of chemical and thermal treatment to begin an abbreviated chemical pulping process, followed immediately by a mechanical treatment to separate the fibres. These hybrid methods include thermomechanical pulping, also known as TMP, and chemithermomechanical pulping, also known as CTMP. The chemical and thermal treatments reduce the amount of energy subsequently required by the mechanical treatment, and also reduce the amount of strength loss suffered by the fibres.
Dissolving pulp or dissolving-grade pulp is a chemical bleached pulp with a high cellulose content enough to be suitable for the production or regenerated cellulose and cellulose derivatives. Dissolving pulp has special properties, such as a high level of brightness and uniform molecular-weight distribution. Dissolving pulp is manufactured for uses that require a high chemical cellulose purity, and particularly low hemicellulose content, since the chemically similar hemicellulose can interfere with subsequent processes. Dissolving pulp is so named because it is not made into paper, but dissolved either in a solvent or by derivatization into a homogeneous solution, which makes it completely chemically accessible and removes any remaining fibrous structure. Once dissolved, it can be spun into textile fibers (such as viscose or Lyocell), or chemically reacted to produce derivatized celluloses, such as cellulose triacetate, a plastic-like material formed into fibers or films, or cellulose ethers such as methyl cellulose, used as a thickener.
An object of the present invention is to upgrade paper-grade pulp (unbleached or partially bleached or fully bleached or bleached market pulp) by removal of hemicelluloses e.g. into dissolving-grade pulp using a combination of enzyme treatment, hot caustic extraction (HCE) and optionally one or more bleaching steps.
HCE has previously only been used as a purification process for sulphite-based production of dissolving pulps and has been considered to not contribute much to the purity of pulps produced from alkaline cooking processes, such as soda and kraft. The other existing alkaline purification process is cold caustic extraction (CCE) which is operated close to room temperature (<40° C.) and at very high sodium hydroxide concentration (1.2-3.0 M equivalent to 5-12% w/w in the liquid phase), while the hot purification process (HCE) is usually run at 70-130° C. and at low NaOH concentration (0.1-0.4 M equivalent to 0.4-1.4% w/w in the liquid phase and typically <0.25 M equivalent to <1.0% w/w in the liquid phase).
The present invention enables the use of HCE as a purification process in the fiberline of an alkaline based pulping process for removal of hemicelluloses e.g. for the production of dissolving pulp through the combined use of a prior enzymatic-stage with hemicellulases.
WO9816682 A2 discloses a process for upgrading paper-grade wood pulp to dissolving-grade pulp by using caustic extraction and xylanase treatments in combination in different steps. However, the concentration range of NaOH disclosed in WO9816682 A2 is very high ranging from 8-12% w/w which is within the same NaOH dosage range as carried out in cold caustic extraction (CCE) but using a non-conventional high temperature of 50-100° C.
The combination of enzyme-treatment with hemicellulases and hot caustic extraction (0.03 g NaOH/g pulp, 80° C., 1 h, 2.5% pulp consistency) was studied by Christov and Prior 1994 (Appl Microbiol Biotechnol 42:492-498) but for acid sulphite pulps and using lower NaOH concentration (0.02M) at low consistency.
In the present invention, the use of an enzyme-stage with hemicellulases can activate the alkaline pulp, such as kraft pulp, for the alkaline purification process in the HCE-stage. The hemicellulases will generate a significant amount of new reducing end groups in the hemicelluloses which in turn can trigger alkaline endwise peeling reactions under the high temperature and alkalinity conditions that can be found in the following HCE-stages.
Wood pulp requires extensive purification before it is suitable for making man-made textile cellulosic fibers (regenerated cellulose) such as viscose, and for making cellulose derivatives, such as esters or ethers. This type of pulp referred as dissolving grade-pulp can be produced by i) acid sulfite pulping followed by bleaching and possibly additional purification processes or ii) by pre-hydrolysis-kraft pulping followed by bleaching and possibly additional purification processes.
The additional purification, which involves treatment with alkali to remove and destroy hemicelluloses and bleaching to remove and destroy lignin reduces the yield and increases the cost of a “dissolving-grade” cellulose derived from wood pulp. The invention provides a method for upgrading paper-grade alkaline pulp e.g. into dissolving-grade pulp using a combination of enzyme treatment and hot caustic extraction.
The invention relates to a method (termed “Method I”) for removal of hemicelluloses (partly or completely) from paper-grade alkaline pulp comprising the steps of
The invention further relates to a method (termed “Method II) for removal of hemicelluloses from paper-grade alkaline pulp comprising the steps of
Hemicelluloses used in Method I or II can comprise xylan and/or mannan.
Method I can in one embodiment be used for production of dissolving-grade pulp.
Preferably one or more hemicellulases used in step i) in Method I or II comprise or consist of one or more xylanases. In another preferred embodiment the one or more hemicellulases used in step i) in Method I or II comprise or consist of one or more mannanases. In a specific embodiment a mannanase is required when the paper-grade alkaline pulp contains mannan.
In a specific embodiment the one or more xylanases used in step i) in Method I or II can be selected from the group consisting of SEQ ID NO: 4 and SEQ ID NO: 5. The one or more xylanases used in step i) in Method I or II can have a sequence identity of at least 60% [such as at least 65%, such as at least 70%, such as at least 75%, such as at least 80%, such as at least 85%, such as at least 90%, such as at least 95%, such as at least 99%] with one or more xylanases selected from the group consisting of SEQ ID NO: 4 and SEQ ID NO: 5.
In another specific embodiment the one or more mannanases used in step i) in Method I or II can be selected from the group consisting of SEQ ID NO: 1, SEQ ID NO: 2, SEQ ID NO: 3, SEQ ID NO: 6 and SEQ ID NO: 7. The one or more mannanases used in step i) in Method I or II can have a sequence identity of at least 60% [such as at least 65%, such as at least 70%, such as at least 75%, such as at least 80%, such as at least 85%, such as at least 90%, such as at least 95%, such as at least 99%] with one or more mannanases selected from the group consisting of SEQ ID NO: 1, SEQ ID NO: 2, SEQ ID NO: 3, SEQ ID NO: 6 and SEQ ID NO: 7.
The one or more hemicellulases used in step i) in Method I or II can also comprise one or more xylanases and one or more mannanases.
The concentration of the one or more hemicellulases used in step i) in Method I or II is preferably from 0.05 mg/kg oven dry pulp to 100 mg/kg oven dry pulp. The alkali source used in step ii) in Method I or II can in a preferred embodiment consist of or comprise NaOH. The alkali source used in step ii) in Method I or II can also consist of or comprise one or more alkali sources selected from the group consisting of NaOH, Ca(OH)2, NH4OH and Mg(OH)2. The hot caustic extraction in step ii) in Method I or II can be performed with a NaOH concentration of less than 1 M, such as less than 0.5 M or such as less than 0.1 M. In one embodiment hot caustic extraction in step ii) in Method I or II is performed at a temperature between 80° C. and 130° C. such as between 90° C. and 110° C.
The paper-grade alkaline kraft pulp can be selected from the group consisting of alkaline hardwood pulp, alkaline softwood pulp, kraft pulp, hardwood kraft pulp, softwood kraft pulp, soda pulp, hardwood soda pulp and softwood soda pulp, or any mixture thereof.
The hemicellulose content of the pulp obtained by Method I or II such as a dissolving-grade pulp can in one embodiment be less than 10%, such as less than 5%, such as less than 4%, such as less than 3%, such as less than 2% or such as less than 1%.
In a preferred embodiment step i) in Method I or II is performed prior to step ii).
In a specific embodiment of Method I or II the paper-grade alkaline pulp is softwood pulp or a mixture of softwood and hardwood pulp and the one or more hemicellulases comprises or consists of one or more xylanases and one or more mannanases.
In a specific embodiment of Method I or II the paper-grade alkaline pulp contains or comprises mannan and the one or more hemicellulases comprises or consists of one or more xylanases and one or more mannanases.
In a preferred embodiment of Method II the method comprises a sequence of stages selected from the group consisting of X-HCE, X-D-HCE, X-D-HCE-X-HCE-D, X-D-HCE-X-D-HCE-D, X-Z-HCE, X-D-HCE-X-HCE-Z, X-Z-HCE-X-HCE-D, X-Paa-HCE, X-D-HCE-X-HCE-Paa and X-Paa-HCE-X-HCE-D (wherein in X is the enzyme stage—i.e. treatment with one or more hemicellulases; HCE is the hot caustric extraction stage as defined elsewhere herein and D is a bleaching stage with chlorine dioxide). The D stage described above in Method II can instead of a chlorine dioxide bleaching be treatment with other oxidizing agents such as chlorine, oxygen, hydrogen peroxide, ozone or peracetic acid, a reducing agent or any combination of these bleaching methods.
The invention further relates to a pulp such as a dissolving-grade pulp made by the method according to the invention (Method I or II) and to textile fibers (regenerated cellulose) made of said dissolving pulp.
Use of said dissolving-grade pulp for textile production and use of the dissolving-grade pulp according to the invention for production of textile fibers is also within the scope of the invention. Finally, the invention relates to use of the dissolving-grade pulp according to the invention for production of derivatized celluloses (cellulose derivatives).
The invention relates to a method for upgrading paper-grade pulp by removal of hemicelluloses e.g. into dissolving-grade pulp using a combination of enzyme treatment, hot caustic extraction and optionally one or more bleaching steps.
The invention relates to a method (termed “Method I”) for removal of hemicelluloses (partly or completely) from paper-grade alkaline pulp comprising the steps of
The invention further relates to a method (termed “Method II) for removal of hemicelluloses from paper-grade alkaline pulp comprising the steps of
Method I can in one embodiment be used for production of dissolving-grade pulp.
Details concerning specific embodiments regarding step i) and step ii) in “Method I” or “Method II” are given herein below.
In a preferred embodiment step i) is performed prior to step ii) in “Method I” or “Method II”.
Use of Hemicellulolytic Enzyme or Hemicellulases in Step i) in “Method I” or “Method II”:
The one or more hemicellulolytic enzyme or hemicellulases used in step i) in “Method I” or “Method II” is further exemplified herein below.
“Hemicellulolytic enzyme” or “hemicellulase” means one or more (e.g., several) enzymes that hydrolyze a hemicellulosic material. See, for example, Shallom and Shoham, Current Opinion In Microbiology, 2003, 6(3): 219-228). Hemicellulases are key components in the degradation of plant biomass. Examples of hemicellulases include, but are not limited to, an acetylmannan esterase, an acetylxylan esterase, an arabinanase, an arabinofuranosidase, a coumaric acid esterase, a feruloyl esterase, a galactosidase, a glucuronidase, a glucuronoyl esterase, a mannanase, a mannosidase, a xylanase, and a xylosidase. The substrates for these enzymes, hemicelluloses, are a heterogeneous group of branched and linear polysaccharides that are bound via hydrogen bonds to the cellulose microfibrils in the plant cell wall, crosslinking them into a robust network. Hemicelluloses are also covalently attached to lignin, forming together with cellulose a highly complex structure. The variable structure and organization of hemicelluloses require the concerted action of many enzymes for its complete degradation. The catalytic modules of hemicellulases are either glycoside hydrolases (GHs) that hydrolyze glycosidic bonds, or carbohydrate esterases (CEs), which hydrolyze ester linkages of acetate or ferulic acid side groups. These catalytic modules, based on homology of their primary sequence, can be assigned into GH and CE families. Some families, with an overall similar fold, can be further grouped into clans, marked alphabetically (e.g., GH-A). A most informative and updated classification of these and other carbohydrate active enzymes is available in the Carbohydrate-Active Enzymes (CAZy) database. Hemicellulolytic enzyme activities can be measured according to Ghose and Bisaria, 1987, Pure & Appl. Chem. 59: 1739-1752, at a suitable temperature such as 40° C.−80° C., e.g., 50° C., 55° C., 60° C., 65° C., or 70° C., and a suitable pH such as 4-9, e.g., 5.0, 5.5, 6.0, 6.5, or 7.0.
Use of Xylanases in Step i) in “Method I” or “Method II”:
The one or more hemicellulases used in step i) in “Method I” or “Method II” can comprise or consist of one or more xylanases. The one or more xylanases used in step i) in “Method I” or “Method II” can be selected from the group consisting of SEQ ID NO: 4 and SEQ ID NO: 5.
The one or more xylanases used in step i) in “Method I” or “Method II” can have a sequence identity of at least 60% (such as at least 65%, such as at least 70%, such as at least 75%, such as at least 80%, such as at least 85%, such as at least 90%, such as at least 95%, such as at least 99%) with one or more xylanases selected from the group consisting of SEQ ID NO: 4 and SEQ ID NO: 5.
The one or more xylanases used in step i) in “Method I” or “Method II” is further exemplified herein below.
A xylanase, as may optionally be used in the present invention, is an enzyme classified as EC 3.2.1.8. The official name is endo-1,4-beta-xylanase. The systematic name is 1,4-beta-D-xylan xylanohydrolase. Other names may be used, such as endo-(1-4)-beta-xylanase; (1-4)-beta-xylan 4-xylanohydrolase; endo-1,4-xylanase; xylanase; beta-1,4-xylanase; endo-1,4-xylanase; endo-beta-1,4-xylanase; endo-1,4-beta-D-xylanase; 1,4-beta-xylan xylanohydrolase; beta-xylanase; beta-1,4-xylan xylanohydrolase; endo-1,4-beta-xylanase; beta-D-xylanase. The reaction catalysed is the endohydrolysis of 1,4-beta-D-xylosidic linkages in xylans.
According to CAZy(ModO), xylanases are presently classified in either of the following Glycoside Hydrolyase Families: 10, 11, 43, 5, or 8.
In an embodiment, the xylanase is derived from a bacterial xylanase, e.g. a Bacillus xylanase, for example from a strain of Bacillus halodurans, Bacillus pumilus, Bacillus agaradhaerens, Bacillus circulans, Bacillus polymyxa, Bacillus sp., Bacillus stearothermophilus, or Bacillus subtilis, including each of the Bacillus xylanase sequences entered at the CAZy(ModO) site.
In a further particular embodiment the family 11 glycoside hydrolase is a fungal xylanase. Fungal xylanases include yeast and filamentous fungal polypeptides as defined above, with the proviso that these polypeptides have xylanase activity.
Examples of fungal xylanases of family 11 glycoside hydrolase are those which can be derived from the following fungal genera: Aspergillus, Aureobasidium, Emericella, Fusarium, Gaeumannomyces, Humicola, Lentinula, Magnaporthe, Neocallimastix, Nocardiopsis, Orpinomyces, Paecilomyces, Penicillium, Pichia, Schizophyllum, Talaromyces, Thermomyces, Trichoderma.
Examples of species of these genera are listed below in the general polypeptide section. The sequences of xylanase polypeptides deriving from a number of these organisms have been submitted to the databases GenBank/GenPept and SwissProt with accession numbers which are apparent from the CAZy(ModO) site.
A preferred fungal xylanase of family 11 glycoside hydrolases is a xylanase derived from
A preferred xylanase is the Thermomyces xylanase described in WO 96/23062.
Various Aspergillus xylanases are also described in EP 695349, EP 600865, EP 628080, and EP 532533. EP 579672 describes a Humicola xylanase.
Preferably, the amino acid sequence of the xylanase has at least 60% identity, preferably at least 65% identity, more preferably at least 70% identity, more preferably at least 75% identity, more preferably at least 80% identity, more preferably at least 85% identity, more preferably at least 90% identity, even more preferably at least 95% identity, and most preferably at least 97% identity to the amino acid sequence of a Bacillus agaradhaerens xylanase (such as SEQ ID NO: 4) or the amino acid sequence of a Dictyoglomus thermophilum xylanase (such as SEQ ID NO: 5).
In an embodiment, the amino acid sequence of the xylanase has one or several substitutions and/or deletions and/or insertions compared to SEQ ID NO: 4 or SEQ ID NO: 5. In particular, the amino acid sequence of the xylanase is identical to SEQ ID NO: 4 or SEQ ID NO: 5.
Xylanase activity can be measured using any assay, in which a substrate is employed, that includes 1,4-beta-D-xylosidic endo-linkages in xylans. Assay-pH and assay-temperature are to be adapted to the xylanase in question.
Different types of substrates are available for the determination of xylanase activity e.g. Xylazyme cross-linked arabinoxylan tablets (from MegaZyme), or insoluble powder dispersions and solutions of azo-dyed arabinoxylan.
Use of Mannanases in Step i) in “Method I” or “Method II”:
The one or more hemicellulases used in step i) in “Method I” or “Method II” can comprise or consist of one or more mannanases. The one or more mannanases used in step i) in “Method I” or “Method II” can be selected from the group consisting of SEQ ID NO: 1, SEQ ID NO: 2, SEQ ID NO: 3, SEQ ID NO: 6 and SEQ ID NO: 7. The one or more mannanases used in step i) in “Method I” or “Method II” has in a preferred embodiment a sequence identity of at least 60% (such as at least 65%, such as at least 70%, such as at least 75%, such as at least 80%, such as at least 85%, such as at least 90%, such as at least 95%, such as at least 99%) with one or more mannanases selected from the group consisting of SEQ ID NO: 1, SEQ ID NO: 2, SEQ ID NO: 3, SEQ ID NO: 6 and SEQ ID NO: 7. The one or more mannanases used in step i) in “Method I” or “Method II” is further exemplified herein below.
The term “mannanase” means a polypeptide having mannan endo-1,4-betamannosidase activity (EC 3.2.1.78) that catalyzes the hydrolysis of 1,4-β-D-mannosidic linkages in mannans, galactomannans and glucomannans. Alternative names of mannan endo-1,4-betamannosidase are 1,4-β-D-mannan mannanohydrolase; endo-1,4-β-mannanase; endo-β-1,4-mannase; β-mannanase B; β-1,4-mannan 4-mannanohydrolase; endo-β-mannanase; and β-D-mannanase. For purposes of the present invention, mannanase activity may be determined using the Reducing End Assay as described in the experimental section. In one aspect, the polypeptides of the present invention have at least 20%, e.g., at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 100% of the mannanase activity of the mature polypeptide of SEQ ID NO: 1 and/or the mature polypeptide of SEQ ID NO: 2 and/or the mature polypeptide of SEQ ID NO: 3 and/or the mature polypeptide of SEQ ID NO: 6 and/or the mature polypeptide of SEQ ID NO: 7.
In a further embodiment the one or more hemicellulases used in step i) in “Method I” or “Method II” can comprise one or more xylanases and one or more mannanases.
Temperature Used in Step i) in “Method I” or “Method II”:
The temperature used for step i) in “Method I” or “Method II” is typically from 20° C. to 100° C. such as a temperature interval selected from the group consisting of from 20° C. to 30° C., from 30° C. to 40° C., from 40° C. to 50° C., from 50° C. to 60° C., from 60° C. to 70° C., from 70° C. to 80° C., from 80° C. to 90° C., from 90° C. to 100° C., or any combination of these intervals.
Incubation Time Used in Step i) in “Method I” or “Method II”:
The incubation time used for step i) in “Method I” or “Method II” is typically from 5 minutes to 6 hours such as a time interval selected from the group consisting of from 5 minutes to 15 minutes, from 15 minutes to 30 minutes, from 30 minutes to 45 minutes, from 45 minutes to 60 minutes, from 1 hour to 1.5 hours, from 1.5 hours to 2 hours, from 2 hours to 2.5 hours, from 2.5 hours to 3 hours, from 3 hours to 3.5 hours, from 3.5 hours to 4 hours, from 4 hours to 4.5 hours, from 4.5 hours to 5 hours, from 5 hours to 5.5 hours, from 5.5 hours to 6 hours, or any combination of these time intervals.
Enzyme Concentration Used in Step i) in “Method I” or “Method II”:
The concentration of the one or more hemicellulases used in step i) in “Method I” or “Method II” can in one embodiment be from 0.05 mg/kg oven dry pulp to 100 mg/kg oven dry pulp such as a concentration selected from the group consisting of from 0.05 mg/kg oven dry pulp to 0.25 mg/kg oven dry pulp, from 0.25 mg/kg oven dry pulp to 1.0 mg/kg oven dry pulp, from 1.0 mg/kg oven dry pulp to 5.0 mg/kg oven dry pulp, from 5.0 mg/kg oven dry pulp to 10.0 mg/kg oven dry pulp, from 10.0 mg/kg oven dry pulp to 15.0 mg/kg oven dry pulp, from 15.0 mg/kg oven dry pulp to 20.0 mg/kg oven dry pulp, from 20.0 mg/kg oven dry pulp to 30.0 mg/kg oven dry pulp, from 30.0 mg/kg oven dry pulp to 40.0 mg/kg oven dry pulp, from 40.0 mg/kg oven dry pulp to 60.0 mg/kg oven dry pulp, from 60.0 mg/kg oven dry pulp to 80.0 mg/kg oven dry pulp, and from 80.0 mg/kg oven dry pulp to 100.0 mg/kg oven dry pulp, or any combination of these intervals.
Hot Caustic Extraction (HCE) in Step ii) in “Method I” or “Method II”:
Hot Caustic Extraction (HCE) is a method to remove short chain hemicellulose and amorphous cellulose in pulps. In a (HCE)-stage the NaOH-concentration is not as high as in a cold alkali treatment, but the temperature is higher.
The temperature in HCE in step ii) in “Method I” or “Method II” is preferably from 70° C. and 160° C. In a preferred embodiment the HCE temperature can be within a temperature interval selected from the group consisting of from about 70° C. to about 75° C., from about 75° C. to about 80° C., from about 80° C. to about 85° C., from about 85° C. to about 90° C., from about 90° C. to about 95° C., from about 95° C. to about 100° C., from about 100° C. to about 105° C., from about 105° C. to about 110° C., from about 110° C. to about 115° C., from about 115° C. to about 120° C., from about 120° C. to about 125° C., from about 125° C. to about 130° C., from about 130° C. to about 135° C., from about 135° C. to about 140° C., from about 140° C. to about 145° C., from about 145° C. to about 150° C., from about 150° C. to about 155° C., and from about 155° C. to about 160° C., or any combination of these intervals. If a temperature of 100° C. or above 100° C. is used the reaction is preferably performed at a pressure above atmospheric pressure such as at a pressure selected from the group consisting of pressure intervals from 1-2 bars, 2-3 bars, 3-4 bars, 4-5 bars, 5-6 bars, 6-7 bars, 7-8 bars, 8-9 bars or 9-10 bars or 10-12 bars or any combination of these intervals.
In a preferred embodiment the alkali source used in step ii) in “Method I” or “Method II” consists of or comprises NaOH. In another embodiment the alkali source used in step ii) consists of or comprises one or more alkali sources selected from the group consisting of NaOH Ca(OH)2, NH4OH and Mg(OH)2.
The hot caustic extraction in step ii) in “Method I” or “Method II” is in a preferred embodiment performed with an alkaline source (such as NaOH) at a concentration in the liquid phase of less than 2 w/w %, such as less than 1.8 w/w %, such as less than 1.6 w/w %, such as less than 1.4 w/w %, such as less than 1.2 w/w %, such as less than 1.0 w/w %, such as less than 0.8 w/w %, such as less than 0.6 w/w %, such as less than 0.4 w/w %, such as less than 0.2 w/w %, or such as less than 0.15 w/w %.
The hot caustic extraction in step ii) in “Method I” or “Method II” is in a preferred embodiment performed with an alkaline source (such as NaOH) consisting of or comprising hydroxide ions (such as NaOH) and the HCE is performed at a concentration of hydroxide ions in the liquid phase of less than 1 M, such as less than 0.9 M, such as less than 0.8 M, such as less than 0.7 M, such as less than 0.6 M, such as less than 0.5 M, such as less than 0.4 M, such as less than 0.3 M, such as less than 0.2 M, such as less than 0.1 M, such as less than 0.09 M, such as less than 0.08 M, such as less than 0.07 M, such as less than 0.06 M, such as less than 0.05 M, such as less than 0.04 M, such as less than 0.03 M and such as less than 0.02 M.
The NaOH concentration in the liquid phase used in the HCE in step ii) in “Method I” or “Method II” is typically less than 2 w/w %, such as less than 1.8 w/w %, such as less than 1.6 w/w %, such as less than 1.4 w/w %, such as less than 1.2 w/w %, such as less than 1.0 w/w %, such as less than 0.8 w/w %, such as less than 0.6 w/w %, such as less than 0.4 w/w %, such as less than 0.2 w/w %, or such as less than 0.15 w/w %.
The hot caustic extraction in step ii) in “Method I” or “Method II” is in a preferred embodiment performed with NaOH as the alkaline source and the HCE is performed at a concentration of NaOH in the liquid phase of less than 1 M, such as less than 0.9 M, such as less than 0.8 M, such as less than 0.7 M, such as less than 0.6 M, such as less than 0.5 M, such as less than 0.4 M, such as less than 0.3 M, such as less than 0.2 M, such as less than 0.1 M, such as less than 0.09 M, such as less than 0.08 M, such as less than 0.07 M, such as less than 0.06 M, such as less than 0.05 M, such as less than 0.04 M, such as less than 0.03 M and such as less than 0.02 M.
The hot caustic extraction in step ii) in “Method I” or “Method II” is in a preferred embodiment performed with an alkaline source (such as NaOH) at a concentration in the liquid phase-selected from the group consisting of from 0.1 w/w % to 0.2 w/w %, from 0.2 w/w % to 0.4 w/w %, from 0.4 w/w % to 0.6 w/w %, from 0.6 w/w % to 0.8 w/w %, from 0.8 w/w % to 1.0 w/w %, from 1.0 w/w % to 1.2 w/w %, from 1.2 w/w % to 1.4 w/w %, from 1.4 w/w % to 1.6 w/w %, from 1.6 w/w % to 1.8 w/w %, from 1.8 w/w % to 2.0 w/w %, or any combination of these intervals ( ).
The hot caustic extraction in step ii) in “Method I” or “Method II” is in a preferred embodiment performed with a NaOH concentration in the liquid phase selected from the group consisting of from 0.1 w/w % to 0.2 w/w %, from 0.2 w/w % to 0.4 w/w %, from 0.4 w/w % to 0.6 w/w %, from 0.6 w/w % to 0.8 w/w %, from 0.8 w/w % to 1.0 w/w %, from 1.0 w/w % to 1.2 w/w %, from 1.2 w/w % to 1.4 w/w %, from 1.4 w/w % to 1.6 w/w %, from 1.6 w/w % to 1.8 w/w %, from 1.8 w/w % to 2.0 w/w %, or any combination of these intervals().
The hot caustic extraction in step ii) in “Method I” or “Method II” is in a preferred embodiment performed with an alkaline source (such as NaOH) at a concentration in the liquid phase of hydroxide ions selected from the group consisting of from 0.01 M to 0.025 M, from 0.025 M to 0.05 M, from 0.05 M to 0.1 M, from 0.1 M to 0.2 M, from 0.2 M to 0.3 M, from 0.3 M to 0.4 M, from 0.4 M to 0.5 M and from 0.5 M to 1 M, or any combination thereof.
The retention time for the HCE in step ii) in “Method I” or “Method II” is typically from 15 minutes to 5 hours. In a preferred embodiment the HCE retention time is within a time interval selected from the group consisting of from 15 minutes to 30 minutes, from 30 minutes to 45 minutes, from 45 minutes to 1 hour, from 1 hour to 1.5 hours, from 1.5 hour to 2 hours, from 2 hour to 2.5 hours, from 2.5 hour to 3 hours, from 3 hour to 3.5 hours, from 3.5 hour to 4 hours, from 4 hour to 4.5 hours, and from 4.5 hour to 5 hours, or any combination of these intervals.
Typical pulp consistencies used for the (HCE)-stage in step ii) in “Method I” or “Method II” is within the range between 2% and 30%. Preferably the pulp consistency used for the HCE in step ii) in “Method I” or “Method II” is from 5% to 20%, such as from 10% to 15%. In a preferred embodiment the pulp consistency used for HCE in step ii) in “Method I” or “Method II” is within an interval selected from the group consisting of from 2% to 4%, from 4% to 6%, from 6% to 8%, from 8% to 10%, from 10% to 12%, from 12% to 14%, from 14% to 16%, from 16% to 18%, from 18% to 20%, from 20% to 22%, from 22% to 24%, from 24% to 26%, from 26% to 28%, and from 28% to 30%, or any combination of these intervals.
Pulp Used and Produced in the Method According to the Invention:
The paper-grade pulp used in the present invention can be wood pulp coming e.g. from softwood trees (such as spruce, pine, fir, larch and hemlock) and/or hardwoods (such as eucalyptus, aspen and birch) or other plant sources such as bamboo.
In a preferred embodiment the paper-grade alkaline pulp is selected from the group consisting of paper-grade kraft hardwood pulp, paper-grade kraft softwood pulp, paper-grade soda hardwood pulp or paper-grade soda softwood pulp and any mixture thereof.
In a preferred embodiment the hemicellulose content of the dissolving-grade pulp produced according to the invention is less than 10%, such as less than 9%, such as less than 8%, such as less than 7%, such as less than 6%, such as less than 5%, such as less than 4%, such as less than 3%, such as less than 2% or such as less than 1%.
The invention relates in one embodiment to a pulp such as a dissolving-grade pulp made by the method according to the invention.
The invention further relates to use of the dissolving-grade pulp according to the invention for production of textile fibers. The dissolving-grade pulp produced may be used in the manufacture of regenerated cellulose such as viscose rayon, lyocell and modal fibers.
The invention further relates to use of the dissolving-grade pulp according to the invention for production of derivatized celluloses (cellulose derivatives) such as cellulose esters and ethers.
Performing “Method I” or “Method II” in the Presence of One or More Surfactants
Step i) and/or step ii) in Method I or “Method II” can be performed in the presence of one or more surfactants such as one or more anionic surfactants and/or one or more nonionic surfactants and/or one or more cationic surfactants.
Surfactants can in one embodiment include poly(alkylene glycol)-based surfactants, ethoxylated dialkylphenols, ethoxylated dialkylphenols, ethoxylated alcohols and/or silicone based surfactants.
Examples of poly(alkylene glycol)-based surfactant are poly(ethylene glycol) alkyl ester, poly(ethylene glycol) alkyl ether, ethylene oxide/propylene oxide homo- and copolymers, or poly(ethylene oxide-co-propylene oxide) alkyl esters or ethers. Other examples include ethoxylated derivatives of primary alcohols, such as dodecanol, secondary alcohols, poly[propylene oxide], derivatives thereof, tridecylalcohol ethoxylated phosphate ester, and the like.
Specific presently preferred anionic surfactant materials useful in the practice of the invention comprise sodium alpha-sulfo methyl laurate, (which may include some alpha-sulfo ethyl laurate) for example as commercially available under the trade name ALPHA-STEP™-ML40; sodium xylene sulfonate, for example as commercially available under the trade name STEPANATE™-X; triethanolammonium lauryl sulfate, for example as commercially available under the trade name STEPANOL™-WAT; diosodium lauryl sulfosuccinate, for example as commercially available under the trade name STEPAN™-Mild SL3; further blends of various anionic surfactants may also be utilized, for example a 50%-50% or a 25%-75% blend of the aforesaid ALPHA-STEP™ and STEPANATE™ materials, or a 20%-80% blend of the aforesaid ALPHA-STEP™ and STEPANOL™ materials (all of the aforesaid commercially available materials may be obtained from Stepan Company, Northfield, Ill.).
Specific presently preferred nonionic surfactant materials useful in the practice of the invention comprise cocodiethanolamide, such as commercially available under trade name NINOL™-11CM; alkyl polyoxyalkylene glycol ethers, such as relatively high molecular weight butyl ethylenoxide-propylenoxide block copolymers commercially available under the trade name TOXIMUL™-8320 from the Stepan Company. Additional alkyl polyoxyalkylene glycol ethers may be selected, for example, as disclosed in U.S. Pat. No. 3,078,315. Blends of the various nonionic surfactants may also be utilized, for example a 50%-50% or a 25%-75% blend of the aforesaid NINOL™ and TOXIMUL™ materials.
Specific presently preferred anionic/nonionic surfactant blends useful in the practice of the invention include various mixtures of the above materials, for example a 50%-50% blends of the aforesaid ALPHA-STEP™ and NINOL™ materials or a 25%-75% blend of the aforesaid STEPANATE™ and TOXIMUL™ materials.
Preferably, the various anionic, nonionic and anionic/nonionic surfactant blends utilized in the practice of the invention have a solids or actives content up to about 100% by weight and preferably have an active content ranging from about 10% to about 80%. Of course, other blends or other solids (active) content may also be utilized and these anionic surfactants, nonionic surfactants, and mixtures thereof may also be utilized with known pulping chemicals such as, for example, anthraquinone and derivatives thereof and/or other typical paper chemicals, such as caustics, defoamers and the like.
Preferred Embodiments
Preferred embodiments of the invention are described in the set of items herein below.
Effect of a Xylanase Treatment in Xylan Removal from a Bleached Northern Mixed Hardwood Kraft Paper-Grade Pulp
Bleached northern mixed hardwood kraft pulp in sheet form (dry lap market paper-grade pulp) was soaked in water and disintegrated in a pulp disintegrator (10000 rpm) and then filtered before being used in the experiments. The pulp was then treated with a xylanase (SEQ ID NO: 5; denoted as X-stage) at 10% consistency, 75° C. and pH 4.5 (acetate buffer) for 4 h using 20 mg enzyme protein (EP)/kg odp (oven-dry pulp; dry matter basis). The pulp suspension was incubated in sealed polyethylene plastic bags immersed in a temperature controlled water bath. After incubation, the pulp was filtered and the filtrate collected. The pulp was then washed and filtered in three consecutive steps with 2 L of warm tap water and 1 L of deionized water. Control experiments were run in parallel under exactly the same conditions except for the use of xylanase.
Part of the washed pulp was then oven-dried at 40° C. and was grinded using a MF 10 basic Microfine grinder drive (IKA) coupled with a cutting-grinding head and a sieve of 2 mm for particle size filtering.
The grinded pulp was used to assess its monossacharide composition after sulfuric acid hydrolysis according to the corresponding description found in NREL Laboratory Analytical Procedure “Determination of Structural Carbohydrates and Lignin in Biomass” (NREL/TP-510-42618). The pulp hydrolysates were analysed by high-performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD) using a CarboPac 1 column and as eluents 0.5 M NaOH (for regeneration of the column) and 50 mM NaOH (4% for 30 min). Monosaccharides were quantified after suitable dilutions against a 5-point standard curve of arabinose (Ara), galactose (Gal), glucose (Glc) and mannose (Man) between 0.002-0.02 g/L.
The results presented regarding monosaccharide composition in Table 1 and in the remainder are the relative percentage (w/w; polymeric sugar concentration) corresponding to the major monossacharides contained in the northern mixed bleached hardwood pulp. It is observed a modest decrease in the content of xylose in the bleached mixed hardwood kraft pulp after the xylanase treatment.
Effect of a Xylanase Treatment Combined with Hot Caustic Extraction in Xylan Removal from a Mixed Hardwood Kraft Paper-Grade Pulp
The same pulps produced in Example 1 (control and xylanase treated) were further submitted to a hot alkaline extraction (HCE) stage at 10% consistency, 95° C. for 2 h and using different NaOH dosages. The NaOH dosages are presented both in terms of the dry-matter content (% odp—oven dry pulp) and in terms of NaOH concentration in the liquid phase of the pulp suspension at 10% consistency. After treatment, the filtrates were collected and the pulps were thoroughly washed with hot tap water. The pulps were then dried in the oven at 40° C. as described in Example 1.
The alkaline extraction performance was firstly evaluated based on the COD (chemical oxygen demand) of the pulp filtrates as shown in Table 2. The COD determination was performed using a COD Cell Test from Merck. The reaction cells with the diluted filtrate were put in a thermo reactor at 148° C. for 2 h and then allowed to cool down before measurement in the photometer NOVA 60 within 60 min after the reaction.
In Table 2 it is observed a clear synergy with regard to the combination of the xylanase and HCE treatment on the amount of COD generated. This is further confirmed in Table 3 in terms of monossacharide composition of the HCE-treated pulps using 4% odp NaOH (0.111 M or 4.44 g/L), where a clear synergy between the xylanase treatment (X-stage) and the hot caustic extraction (HCE-stage) is visible: the X-HCE treatment with 4% odp NaOH allows a high amount of xylan removal down to 13.4% (ca. 39% removal) when compared to the control treatment where it almost did not affect its xylan content. A further decrease in the amount of xylan can be anticipated if the treatment is repeated as illustrated in Examples 6 and 7 for the cases of oxygen-delignified hardwood pulp and unbleached softwood pulp where longer sequences comprising X and HCE treatments resulted in less then 10% of residual hemicelluloses in pulp.
Effect of a Xylanase Treatment Combined with HCE in Xylan Removal from a Chlorine Dioxide Delignified Northern Mixed Hardwood Kraft Paper-Grade Pulp (Partially Bleached with O-D0-Stages): O-D0-X-HCE Sequence
A previously oxygen and chlorine dioxide delignified northern mixed hardwood kraft pulp (O-D0-pulp; paper-grade pulping and bleaching process) was treated with xylanase (SEQ ID NO: 5) under the same conditions as in Example 1. The control and the xylanase treated pulp was further treated with HCE as described in Example 2 but using 6% odp NaOH (0.167 M or 6.67 g/L) and 12% odp NaOH (0.333 M or 13.3 g/L) and higher temperatures.
In the cases where higher temperature than 95° C. were used, the HCE treatments were conducted in steel beakers that were pressurized at room temperature with N2 until 1.5 and 2.0 bar for the experiments at 105° C. and 115° C., respectively. These beakers were placed inside the Labomat BFA-24 (Werner Mathis AG, Switzerland) which is an instrument that allows controlling temperature, mechanical agitation and treatment time of the reaction systems in the beakers. The instrument is controlled by the Univision S software (Univision S “BFA” Programming Instruction, version 2.0 edition 07/2006 by Werner Mathis AG, Switzerland). Beaker temperature is increased by heat transfer from an infrared-radiation unit. Beakers are cooled down by cooling the air in a heat exchanger with a cooling water supply.
The results presented in Table 4 show that xylan is removed from this pulp until a limit of ca. 10.1% (ca. 43% removal). As this original pulp is only partially bleached with O-D0 stages, it is required more bleaching stages (e.g. D, P, Paa, Z or Y) combined with X and HCE purification thus allowing reaching levels of hemicelluloses below 10%, as described in Examples 6 and 7.
Effect of a Xylanase Treatment Combined with HCE in Xylan Removal from an Oxygen Delignified Eucalyptus Kraft Paper-Grade Pulp (Partially Bleached with a O-Stage): O-X-HCE Sequence
A hardwood eucalypt kraft pulp after oxygen delignification was submitted to the same X-HCE treatment as described in the previous examples. In this case, it was possible to reach a xylan content down to 8.5% (ca. 39% removal) as shown in Table 5.
Effect of a Xylanase Treatment Combined with Hot Alkaline Extraction Stages and Chlorine Dioxide Stages in the Bleaching and Purification of an Oxygen Delignified Eucalyptus Kraft Paper-Grade Pulp (Partially Bleached with an O-Stage): O-X-D0-HCE Sequence
An eucalypt kraft pulp after oxygen delignification was submitted to a sequence of treatments in the following order: X-D0-HCE. The X-stage conditions were the same as described in Example 1. The chlorine dioxide treatment (D0-stage) was done at 10% consistency in plastic bags using 1.10% odp ClO2, 80° C., initial pH of 2.5 (adjusted with sulfuric acid) for 90 min. The HCE-stage was performed as before at 95° C. and using 6 and 12% odp NaOH, designated by HCE6 and HCE12, respectively.
The results presented in Table 6 show that it was possible to reach 9.5% of xylan left in the pulp after O-X-D0-HCE sequence confirming the possibility of applying the combination of X and HCE in a more flexible way by having bleaching stages in between the X and HCE treatments for pulp purification (removal of hemicelluloses). This result could be further improved by repeating treatment, for example using X-HCE and possibly comprising a bleaching stage, as described in Examples 6 and 7.
Effect of a Xylanase Treatment Before and within the Pulp Bleaching Process of an Oxygen Delignified Eucalyptus Kraft Paper-Grade Pulp (Partially Bleached with a O-Stage) on Bleaching and Purification (Xylan Removal): O-X-D0-HCE-X-HCE-D1 Sequence
The same eucalypt kraft pulp as in Example 5 was treated with the following sequence of stages at 10% consistency: X-D0-HCE-X-HCE-D1. The X and D0 stages were conducted as in Example 5 but using two dosages of enzyme protein (EP) in the X-stages: 10 and 20 mg EP/kg odp. The hot caustic extraction stages were run at two different temperatures, two different dosages of NaOH and with or without the addition of hydrogen peroxide. The HCE2 and HCE6 stages were run as before in Example 2 at 95° C. for 2 h and using 2 and 6% odp NaOH, respectively. In addition, HCE-stages were run at 85° C. for 2 h, using 1% odp NaOH with or without the co-addition of hydrogen peroxide (0.5% H2O2 odp), HCE1p and HCE1 respectively. In the last chlorine dioxide treatment (D1-stage) it was used 0.4% odp ClO2, pH 4.5-5.0 (adjusted with sulfuric acid), 80° C. for 2 h. After each stage, the pulps were thoroughly washed as described in the previous examples.
Pulp handsheets were prepared according to ISO 3688 for the measurement of the “ISO brightness” (diffuse blue reflectance factor; ISO 2470-1) and using a Color Touch PC spectrophotometer from Technidyne.
In Table 7, it is seen that up to ca. 53% of the xylan was removed from the pulp by using the sequences of stages comprising HCE stages at higher temperature and higher dosage of NaOH (HCE2 and HCE6) thereby reaching a level of 8.0% xylan in the fully bleached pulp. In terms of the final brightness of the bleached pulps, all the xylanase treated pulps exhibit much higher brightness than the controls without enzyme addition. When hydrogen peroxide is not added in the HCE stage, the difference between the xylanase treated pulp and the control is very high (up to 4.5 ISO brightness units) while reaching values≥91% ISO brightness with xylanase addition.
Effect of a Xylanase and Mannanase (X+M) Treatment Combined with Hot Alkaline Extraction Stages and Chlorine Dioxide Stages in the Bleaching and Purification of a Unbleached Softwood Kraft Paper-Grade Pulp: (X+M)-D0-HCE-(X+M)-D1-HCE-D2 Sequence
An unbleached softwood kraft pulp was treated with the following sequence of stages at 10% consistency: (X+M)-D0-HCE-(X+M)-D1-HCE-D2. The enzyme-stage used a xylanase (SEQ ID NO: 5; denoted as X) and a mannanase (SEQ ID NO: 6; denoted as M) either alone or combined (X+M) at 10% consistency at 75° C. and pH 4.5 (acetate buffer) for 4 h and using 10 or 20 mg of each enzyme protein (EP)/kg odp (oven-dry pulp; dry matter basis) for each enzyme. For the D0-stage, it was used 1.50% odp ClO2, 80° C., initial pH of 2.8 (adjusted with sulfuric acid) for 1 h. The D1-stage used 1.50% odp ClO2, 80° C., initial pH of 4.0 (adjusted with sulfuric acid) for 3 h while the D2-stage had 0.4% odp ClO2, 70° C., initial pH of 4.0 (adjusted with sulfuric acid) for 3 h. The HCE-stages were performed as before at 95° C. and using 2 and 6% odp NaOH, designated by HCE2 and HCE6, respectively.
The amount of hemicelluloses in the final bleached pulp reached a level of 7.6% when using the sequence comprising the enzyme stages with xylanase and mannanase combined with HCE6, which represents a removal of 52% of hemicelluloses (xylan and mannan) from the original pulp. An additive effect is seen when combining the xylanase with the mannanase in terms of the extent of xylan and mannan removal and of the final ISO brightness of the bleached pulp when compared to their performance alone. This indicates that for softwood pulps it is important to have both a xylanase and a mannanase in the enzyme-stage (X+M) in order to remove hemicelluloses to a significant extent and upgrade the original paper-pulp into dissolving pulp. This is seen in Table 6 where less than 10% hemicelluloses is reached by such approach comprising (X+M) and HCE purification stages. In fact, for this pulp the sequences with HCE6-stages were more efficient regarding the extent of hemicelluloses removal compared to the sequences with HCE2-stages.
Effect of an Acid Stage (A) Combined with the Enzyme Based Upgrading Process Applied to an Oxygen Delignified Northern Mixed Hardwood Kraft Paper-Grade Pulp
Oxygen delignified northern mixed hardwood kraft pulp was treated with a sequence of stages comprising enzymes (X—xylanase; SEQ ID NO: 5; M—mannanase; SEQ ID NO: 6), hot caustic extraction (HCE at 6% odp NaOH) and chlorine dioxide bleaching (D) as carried out in Example 6: O-(X+M)-D0-HCE6-(X+M)-HCE6-D1. In addition, it was studied the effect of an acid treatment (A-stage) after the first enzyme-stage (X+M). This acid stage was carried out at 10% consistency at an initial pH of 2.0 using sulfuric acid. This A-stage was conducted either at 95° C. for 180 min or at 115° C. for 90 min. When at 95° C., the pulp suspension was put inside a polyethylene bag immersed in a temperature-controlled water bath; as for the experiment at 115° C., the pulp was treated inside a steel beaker pressurized until 2 bar with N2 and then introduced in the Labomat BFA-34 (Werner Mathis AG, Switzerland) oven. After the treatments the pulps were filtered and washed as previously described.
It is seen in Table 9 that the enzyme-based sequence, without the inclusion of the A-stage, allows reaching a level of 12% hemicelluloses in the final O-(X+M)-D0-HCE6-(X+M)-HCE6-D1 treated pulp which corresponds to ca. 46% of hemicelluloses that were removed from the original oxygen deliginified hardwood kraft pulp. When an acid treatment is included in the beginning of the sequences (pre-bleaching), an increased removal of hemicelluloses is obtained up to 53% removal with the more aggressive A-stage at 115° C.
Effect of a Post Cold Caustic Extraction (CCE) Treatment Combined with the Enzyme Based Upgrading Process Applied to an Oxygen Delignified Northern Mixed Hardwood Kraft Paper-Grade Pulp and to a Softwood Kraft Pulp.
The hardwood pulp treated by O-(X+M)-D0-HCE6-(X+M)-HCE6-D1 in the Example 8 was further treated by a cold caustic extraction (CCE) stage at different NaOH concentrations in the liquid phase of the pulp suspension ranging from ca. 22 to 89 g NaOH/L. The CCE-stage was carried out at 10% consistency with the pulp inside polyethylene bags immersed in a water bath at 35° C. for 30 min. The pulp was then filtered and thoroughly washed with water and afterwards acidified with sulfuric acid at 5% consistency until pH was below 5 for 20 min at room temperature. It was finally filtered and kept for further analysis.
In addition, the softwood pulp treated by (X+M)-D0-HCE6-(X+M)-D1-HCE6-D2 in the Example 7 using 20 mg EP/kg odp of each enzyme in the two (X+M) stages was further treated with a CCE stage following the same procedure as described for the hardwood pulp.
In Table 10 can be seen that the enzyme treated pulps always reach a lower amount of hemicelluloses after the CCE stage for both types of pulps. Considering, for example, a target of 4% residual hemicelluloses in the final pulp, then the enzyme-based sequences allow a noteworthy reduction in the amount of NaOH needed. Using a CCE stage at 80% odp NaOH, it was possible to reach a residual content of hemicelluloses below 5% for both pulps which can be considered sufficient to be qualified as a standard viscose-grade dissolving pulp.
| Number | Date | Country | Kind |
|---|---|---|---|
| 15166103 | May 2015 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2015/076668 | 11/16/2015 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2016/079045 | 5/26/2016 | WO | A |
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| 20170350072 A1 | Dec 2017 | US |
