Patent Application
20140273107
Not Applicable
This invention relates to processing of cellulosic solid waste from paper related industries for extraction of fermentable sugars.
Lignocellulosic materials are excellent sources for energy products, platform chemicals and bioplastics. Sugars produced by the degradation of carbohydrate polymers can be fermented into ethanol and butanol as energy sources. Sugars and cellulose degradation compounds can serve as platform chemicals in the production of bulk chemicals and they can also be used as feedstocks for microbial production of plastics such as polyhydrolxyalkanoates.
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Paper mills, especially those recycling old cardboard containers (OCC) produce large quantities of fiber fragments which pass through into the waste stream. These fines are composed primarily of cellulose and hemicellulose (amorphous short chain polymers of substituted hexoses and pentoses). They are the source of substantial bioburden due to their long time decay in the environment. Since they contribute substantially to the oxygen demand in the effluents, they are typically separated and sent to landfills by the paper mills. Current landfilling costs are nearly $60/ton, and thus disposal costs to the paper mills are to the tune of $1.5 million/year based on typical sludge production at an average size paper mills in NY at 100 tons/day.
These costs are projected to increase substantially in the future due to the pressure on landfill space. Therefore there is an acute need to divert the wastes, perhaps extracting value through products which not only are marketable but also reduce the landfill volumes.
The waste stream from recycled paper mills contains cellulosic fines and also particles of mineral origin, typically clay or calcium carbonate from the fillers and coatings used in the waste paper. The cellulosic fines are easily hydrolyzable by either acid or enzymatic processes. In the enzymatic process, a cocktail of cellulose enzymes acts progressively and sequentially to open up the cellulose crystalline structure and depolymerize it, producing monomeric sugars. The sugars are primarily glucose and certain other common hexoses which are fermentable into ethanol, butanol or other advanced energy products. Microbial fermentation can also lead to bioplastics such as polyhydroxyalkanoates.
A sample set of fines rejected from a recycled paper mill was obtained. The composition is presented in Table 1 below.
Though the properties of sludge differ not only for different mills but also at different times at same mill, Table 1 is exemplary of possible conditions. The pH of sludge varies between 6 and 8. Ash content is very high for recycled papermills. The short fibers (mainly cellulose fibers) go to belt filter and then to screw press. In general, the PCS contains very high levels of dry solids because it is rich in hydrophobic fibers. To summarize, PCS is a mixture of cellulose fibre (40-65% of dry solids), printing inks and mineral components (25-40% dry solids: kaolin, talc and calcium carbonate). Due to high fiber content PCS has large amount of carbon (around 50% C dry solids) and mineral matter (clay and calcium carbonate, 5-25% dry solids).
The present technology processes a waste stream comprising cellulosic fines, e.g., from recycled packaging paper mills, into a stream of fermentable sugars. These fermentable sugars may be fermented to yield bioethanol which is of value as a fuel, for production of biodiesel and other alkoxy esters, and/or manufacturers of other products such as bioplastics such as polyhydroxy alkanoates.
According to a preferred embodiment, a process is provided to:
(a) hydrolyze the cellulosic fines found in recycled paper mill waste streams using a commercially available cellulose enzyme formulation;
(b) increase the enzymatic hydrolysis yield by shielding the inert components of the waste stream using a surfactant; and
(c) optimize the surfactant with respect to its composition (anionic, non-ionic or cationic) and dosage.
Recycled containerboard and linerboard paper mills reject significant amounts of cellulosic fines into their waste stream which are eventually landfilled at a cost to the manufacturer and also present a load on the environment. However, it is possible to digest the cellulosic portions of the rejects by enzymatic hydrolysis and thus produce sugars in their monomeric forms. The resulting sugar solutions can be fermented into biofuels such as ethanol and butanol, or processed into biomaterials such as polyhydroxy-alkanoates. The enzymes, however, have may have a competitive binding affinity for inorganic particulates, resulting in a non-specific absorption of some or all types of enzymes to the particles. Indeed, similar high surface area particles are used in the purification of similar enzymes. Therefore, in the presence of inorganic particles, such as precipitated calcium chloride (PCC), the activity and bioavailability of the enzymes may be substantially reduced.
It has been found that surfactants are able to coat the inorganic particulates and otherwise reduce binding of the hydrolytic enzymes, leading to a significant increase in activity, thus saving cost and increasing efficiency. It has been found that effective surfactants do not also block binding or biological activity of the enzymes for the cellulosic particles and components of the solution.
Cationic, non-ionic and anionic surfactants were tested at various dosages. A non-ionic surfactant, Tween 80 (polysorbate 80) was better than the tested cationic and anionic surfactants.
The inorganic particles may be separated from the waste stream, and used as animal bedding or the like.
Some investigators have suggested the use of anaerobic fermentation as a means to degrade and make use of the organic components in the waste stream, but due to presence of large amount of calcium carbonate, kaolin and other fillers, they give rise to problems such as scaling of biomass, reactors and pipes, reduced specific methanogenic activity and loss of buffer capacity, and essential nutrients for anaerobic degradation.
According of the present technology, hydrolysis the cellulosic constituent of PCS and screw press sludge and produce high value fermentable sugars, which permit efficient fermentation to ethanol, and also production of plastics and other useful materials.
The present technology avoids use of membranes or separation tanks to separate inhibitors and thus lowers the cost of separation. It also produces bi-products such as low quality fillers that can be sold to recycled paper mills or animal bedding processors. Because both the organic and inorganic components are separated and made available for downstream use, the amount of burden on landfill is substantially reduced.
Commercially available hydrolysis enzymes include Cellic® HTec3, a concentrated hemicellulase that works alone or in combination with Cellic® CTec3 cellulase enzyme from Novozymes (Denmark).
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Hydrolysis experiments were conducted on two different feedstocks. The first was a simulated waste feedstock, consisting of a sample of unbleached kraft softwood pulp (UBSWKP) that is typical of repulped old corrugated containerboard stocks (OCC). The second was an actual reject fines waste stream from a recycled paper board mill. (Supplied by Minimill LLC, Dewitt N.Y. in conjunction with Greenpak LLC, Niagara Falls N.Y.). The reject stream consisted of cellulosic fines (35%) with the remainder as ash-producing constituents. The non-cellulosic portion contains kaolin and precipitated calcium carbonate fillers from the waste paper and smaller amounts of plastic and other residues.
The non-cellulosic portion of the feedstock acts a competitor for enzyme adsorption, and reduces the net yield and productivity of the hydrolysis per unit enzyme reactant. This leads to increased costs and inefficiencies in the hydrolysis process.
Table 2 below shows the enzymatic hydrolysis yields of a sample of waste fines solids from a recycled paper mill. Although the yields are relatively low, an increase would be expected upon routine optimization with respect to enzyme dosages.
The present approach to resolve this problem is to preferentially or selectively cover the inorganic components with a suitable surfactant so that enzyme binding and action is localized to the cellulosic components. For this purpose, cationic, non-ionic and anionic surfactants were tested at different dosages.
Results are shown for the case of the nonionic surfactant. The ionic surfactants tested were not seen as being as effective as the nonionic surfactant.
A pulp sample (unbleached kraft softwood pulp) was chosen as a model of the OCC pulp.
The numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
The present application is a non-provisional of, and claims benefit of priority under 35 U.S.C. §116(e) from U.S. Provisional Patent Application Ser. No. 61/792,793, filed Mar. 15, 2014, the entirety of which is expressly incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 61792793 | Mar 2013 | US |
