High residual content (HRC) kraft/soda lignin as an ingredient in wood adhesives

Abstract

Most processes currently being proposed and/or used for the production of lignin from kraft or soda black liquors are capable of producing two main types of lignin: high residual content (HRC) lignin and low residual content (LRC) lignin. Surprisingly, it was discovered that HRC lignin, is a suitable ingredient in alkaline adhesives, particularly wood adhesives of the phenolic type (e.g. resole resins). This biomaterial is environmentally green and remarkably low cost, which makes it an industrially viable material to be used as a novel and major ingredient in phenolic adhesives for the manufacture of exterior grade plywood, laminated veneer lumber, oriented strand board (OSB) and other wood productsthis was successfully demonstrated in a number of laboratory experiments as well as several different mill trials. The composition, preparation and application of such wood adhesives are hereby disclosed.

Claims

1. A wood adhesive comprising a residual content of lignin and at least one of i) a formaldehyde; a phenol; and a sodium hydroxide or ii) a phenol formaldehyde resin, wherein the lignin has an ash content of greater than 19.53 to 30 wt % ash, and a pH of greater than 9.66 to 11.2.

2. The wood adhesive of claim 1, wherein the lignin is selected from the group consisting of softwood, hardwood, annual plants and combinations.

3. The wood adhesive of claim 1 wherein the lignin is 0.5 to 50 wt % of the adhesive solids.

4. The wood adhesive of claim 3 wherein the lignin is 2.5 to 30 wt % of the adhesive solids.

5. A method of producing a wood adhesive comprising providing a residual content of lignin, wherein the lignin has an ash content of greater than 19.53 to 30 wt % ash, and a pH of greater than 9.66 to 11.2; and at least one of i) providing a formaldehyde, a phenol and a sodium hydroxide; or ii) providing a phenol formaldehyde resin; mixing the lignin and either i) the sodium hydroxide, formaldehyde and phenol or ii) the phenol formaldehyde resin to produce the adhesive.

6. The method of claim 5 wherein the lignin is 0.5 to 50 wt % of the adhesive.

7. The method of claim 6, wherein the lignin is 2.5 to 30 wt % of the adhesive.

8. An adhesive comprising a residual content of lignin, wherein the lignin has an ash content of greater than 19.53 to 30 wt % ash, and a pH of greater than 9.66 to 11.2, and at least one of the following selected from the group consisting of i) a formaldehyde, a phenol, a sodium hydroxide; ii) a phenol formaldehyde resin; iii) Melamine-Urea-Phenol-Formaldehyde (MUPF) resin; iv) phenol resorcinol formaldehyde (PRF) resin; and combinations thereof.

9. The wood adhesive of claim 1, wherein said lignin is a kraft lignin.

10. The method of claim 5, wherein the lignin is directly produced from a kraft lignin recovery system.

11. The adhesive of claim 8, wherein the lignin is directly produced from a kraft lignin recovery system.

12. The adhesive of claim 10, wherein the kraft lignin recovery system is the LignoForce system.

13. The adhesive of claim 11, wherein the kraft lignin recovery system is the LignoForce system.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1a illustrates a graph of pH versus lignin concentration in 3 wt % NaOH solution where the lignin is Lignoforce HRC lignin and LRC lignin on an Oven Dry (OD) basis wt %;

(2) FIG. 1b illustrates a graph of viscosity versus lignin concentration in 3 wt % NaOH solution where the lignin is Lignoforce HRC lignin and LRC lignin on an Oven Dry (OD) basis wt %;

(3) FIG. 2a illustrates a graph of pH versus lignin concentration in 10 wt % NaOH solution where the lignin is Lignoforce HRC lignin and LRC lignin on an Oven Dry (OD) basis wt %;

(4) FIG. 2b illustrates a graph of viscosity versus lignin concentration in 10 wt % NaOH solution where the lignin is Lignoforce HRC lignin and LRC lignin on an Oven Dry (OD) basis wt %;

(5) FIG. 3a illustrates a graph of pH versus lignin concentration in 10 wt % NaOH solution in the case of HRC lignins generated from oxidized and unoxidized black liquors;

(6) FIG. 3b illustrates a graph of viscosity versus lignin concentration in 10 wt % NaOH solution in the case where HRC lignins are generated from oxidized and unoxidized black liquors;

(7) FIG. 4a illustrates a graph of pH versus lignin concentration in the case of LignoForce HRC lignins dissolved in 3% NaOH and 10% NaOH sodium hydroxide solutions;

(8) FIG. 4b illustrates a graph of viscosity versus lignin concentration in the case of LignoForce HRC lignins dissolved in 3 and 10% sodium hydroxide solutions;

(9) FIG. 5 illustrates a particle size distribution of ground HRC and LRC lignins in water;

(10) FIG. 6 illustrates a graph of shear strength (MPa) versus press temperature ( C.) for four lignin-PF resins at three press temperatures and 90 seconds pressing time using ABES.

DETAILED DESCRIPTION

(11) In an effort to recover lignin from kraft, pre-hydrolysis kraft (dissolving kraft) and soda black liquors, a number of approaches have been considered in the prior art, which mostly use acid addition to precipitate lignin from black liquor. In most of these processes, it is difficult to separate the lignin from the acidified black liquor solutions. Even though these approaches work to a certain extent, the filtration resistance is still quite high leading to unreasonably low filtration rates and, in certain cases, a lignin product of low dry solids content. This, in turn, leads to a large filtration area being required in the equipment needed for lignin filtration leading to high capital costs as well as increased drying costs for the lignin. A second problem associated with most lignin precipitation processes using acid is the large amount of acid (e.g. carbon dioxide and/or sulphuric acid) that is needed to induce the lignin to come out of solution and/or be converted from the sodium to the hydrogen form (e.g. during suspension of the lignin cake in an acid solution or the washing of the lignin with acid on the filter). A third problem associated with most lignin acid precipitation processes is the emission of totally reduced sulphur (TRS) compounds during most stages of the process. Such compounds which include hydrogen sulphide, methyl mercaptan, dimethyl sulphide and dimethyl disulphide are strongly odorous compounds with well-known negative effects on human health and other forms of life.

(12) To eliminate or reduce the risk on human health, reduce the chemical consumption, and improve the lignin filterability, FPInnovations developed a new process called the LignoForce System (U.S. Pat. No. 8,771,464) the description of which is incorporated herein by reference that uses a black liquor oxidation step that converts sulphur species of the TRS such as hydrogen sulphide, methyl mercaptan, dimethyl sulphide and dimethyl disulphide, present in the kraft black liquor, are oxidized to non-volatile species such as thiosulphate and sulphate (in the case of H.sub.2S), methane sulphonic acid (in the case of mercaptan), dimethyl sulphoxide and dimethyl sulphone (in the case dimethylsulphide) and methane sulphonic acid (in the case of dimethyl disulphide). Due to the exothermic nature of these oxidation reactions, the degree of dissociation of the lignin charged groups (e.g. phenolic groups) decreases leading to increased lignin colloid agglomeration and coagulation to form larger lignin particles (and larger particles lead to higher filtration rates). In addition, the acids produced in this step, mainly from TRS and carbohydrates present in the black liquor, lead to a reduction in the pH of the liquor, thereby reducing purchased acid requirements.

(13) A further surprising advantage of the HRC lignin described herein is lower VOC (volatile organic compound) emissions then conventional lignin, and produce less VOC's (especially when heated) in the production of various products (i.e. PF and PF resin adhesive) when compared to conventional lignins.

(14) The recovered lignin could be used in many applications including as an ingredient in phenolic-adhesive formulations.

(15) An HRC (high residual content) lignin is defined as a non-LRC lignin and as such has a high residual inorganic and organic content. There are several categories of HRC lignin. Typical HRC includes an ash content of greater than 12.9 to 30 wt % ash, and a pH of greater than 8 to 11.2.

(16) Water-washed HRC (WWHRC) has an ash content of greater than 6 to 12.9 wt % ash and a pH of greater than 7 to 8.

(17) While a third category of the HRC is Medium Residual Content (MRC) lignin that is partially acid washed and has an ash content of 1.9 to 6 wt % ash and a pH of greater than 3.8 to 7, and preferably from greater than 2 to 6 wt % ash and a pH of greater than 4 to 7.

(18) The HRC lignin can be obtained from softwood, hardwood, (including eucalyptus), or annual plants by using either the kraft, pre-hydrolysis kraft (dissolving kraft) or the soda process. Furthermore, HRC lignin can be recovered from oxidized or un-oxidized black liquor.

(19) HRC lignin can be used in phenolic adhesives as an aqueous alkaline solution, as a wet cake, or as a dry powder.

(20) Phenolic-type adhesive formulations used for manufacturing exterior-grade plywood and laminated veneer lumber typically contain 60-80 wt % of liquid phenol-formaldehyde (PF) resin, 10-15 wt % of additives (usually fillers and extenders such as wheat flour, corncob flour, soda ash, etc.) with the balance being water. The final solids content of the glue mix is in the range of 40-44 wt. %. The addition of additives is aimed at adjusting the rheological performance, moderating glue penetration and distribution on the wood surface, improving the pre-press tack property and dry-out resistance, and reducing costs. The glue mix is produced in a glue mixer by mechanically mixing the phenolic resin with various additives at certain ratios in a certain order for a predefined mixing time.

(21) Adhesive formulation or adhesive solid content weight % for panel making includes resin and may or may not include fillers/extenders, depending on the final application or type of panel. (i.e. adhesive solids include PF resin in the case of OSB panels, MDF and PB, and PF+fillers or additives in the case of plywood and LVL). Adhesive solids weight % is the non-volatile portion after oven-drying under specified oven conditions. The volatile portion is mainly water and/or solvent in the adhesive.

(22) The inventors discovered that HRC lignin which is produced from black liquor is a suitable ingredient in wood adhesives of the phenolic type. This biomaterial is environmentally green and remarkably low cost, which makes it an industrially viable material to be used as a novel and major ingredient in phenolic adhesives for the manufacture of exterior grade plywood, laminated veneer lumber (LVL), oriented strandboard (OSB) and other wood products. In particular, the inventors discovered that HRC lignin can not only replace phenolic resin precursors (e.g. phenol), or phenolic resin (e.g. PF resin), but also fillers and extenders such as wheat flour, corncob flour, bark flour and soda ashthese are usually added in the glue mix used as an adhesive in the manufacturing of exterior-grade plywood panels and laminated veneer lumber.

(23) Surprisingly, the inventors have found that HRC lignin produced from black liquor that was oxidized beyond what is needed to destroy 95% of TRS compounds (e.g. as produced by the patented LignoForce System, U.S. Pat. No. 8,771,464), and hereby referred to as LignoForce lignin), can easily be dissolved and/or dispersed in low-concentration sodium hydroxide solutions (e.g. 3-10 wt %) and/or PF resin formulation media for use in the direct formulation of wood glue mix and the manufacture of lignin-PF resins to be employed as adhesives in various wood products. In contrast to LRC lignin, HRC lignin, and especially HRC lignin from the LignoForce process, was found to exhibit: a) higher solubility and speed of dissolution in phenolic adhesive formulations, b) reduced sodium hydroxide (or sodium carbonate) requirements for achieving the required glue mix pH or resin pH, c) better compatibility with phenol-formaldehyde glue mixes with respect to rheological properties, which are very important to the successful application on wood surfaces of the resin through common industrial glue applicators such as curtain coater, etc., and d) better reactivitythis is despite the fact that such HRC lignins typically contain much higher levels of ash, and other impurities. In addition, the inventors found that the performance of lignin-based PF resins prepared in situ by reaction of phenol, formaldehyde, HRC LignoForce lignin and sodium hydroxide or by post-blending of HRC LignoForce kraft lignin with commercial PF resins, was comparable or better than that of commercial PF resins.

(24) It should be understood here that for the purposes described herein a typical HRC lignin is lignin of a high residual content with a pH close to the pK.sub.a of phenolic hydroxyl groups (pH=10). At this pH, about 50% of the phenolic hydroxyl groups are in the sodium form while the remaining 50% are in the hydrogen (acid) form. It should also be understood, however, that HRC lignin can be obtained at any pH between 8-11 since, at pH 11, lignin begins to precipitate from black liquor and continues to do so until pH 8-9. It should also be understood here, that the pK.sub.a of phenolic hydroxyl groups can vary to a certain extent depending on the substituents on the benzene rings found in lignin. For example, Ragnar et al., in pK.sub.a-values of guaicacyl and syringyl phenols related to lignin, Journal of Wood Chemistry and Technology, 20(3), 277-305 (2000) reported pK.sub.a values between 6.2 and 11.3 for lignin-related phenolic groups. Depending on the precipitation pH, the phenolic hydroxyl groups of HRC lignin will be mostly in the sodium form at pH levels over the pKa of phenolic hydroxyl groups (e.g. pH range: 10-11 assuming a pK.sub.a of 10 for phenolic groups) and mostly in the hydrogen form for precipitation pH levels below the pK.sub.a of phenolic hydroxyl groups (e.g. pH range: 8-10). HRC lignin can be produced at a higher purity and additional favourable properties with respect to its use in phenolic glue applications if, ahead of the black liquor acidification step referred to above, an enhanced black liquor oxidation step is included as, for example, discussed in Kouisni and Paleologou, U.S. Pat. No. 8,771,464 B2, Jul. 8, 2014. This process, called LignoForce, is currently being commercialized. Furthermore, this process allows the production of a range of lignins having different residual organic and inorganic content and consequently different pH values ranging from 2 to 10.

(25) The description herein introduces LignoForce HRC lignin among other HRC lignins as a novel ingredient to be used in phenolic type of alkaline adhesives employed in the manufacture of exterior plywood, laminated veneer lumber, oriented strand board and other wood products. The content of such lignin in plywood glue mix formulations, for example, could be from 0 to 50 wt. %, preferably from 2.5 to 30 wt % of glue mix solids. The lignin as a novel ingredient in the phenolic glue mix is used to substitute the phenolic resin (e.g. PF resin) at substitution levels from 0 to 35 wt %, but preferably from 0 to 25 wt %, and/or substitute the above-mentioned additives (e.g. fillers and extenders such as wheat flour, corncob residue, soda ash, etc.) at substitution levels from 0 to 100 wt %. It is also possible according to the description herein that only one or two of the additives be partially or fully substituted in the phenolic glue mix. The LignoForce HRC lignin can be directly mixed with other ingredients during the production of the phenolic glue mix with no lumps or aggregates forming in the glue mix.

(26) It should be understood here that, for the purposes described herein, HRC-type of lignins can be produced not only from processes that use a press to concentrate the lignin slurry generated from the acidification of black liquor using carbon dioxide or other acids (e.g. LignoForce, LignoBoost and Mead-Westvaco processes). Other lignin-recovery processes which use other lignin concentration approaches such as decantation of the supernatant solution (e.g. Liquid Lignin Process as described in Michael A. Lake, and John C. Blackburn, Process for recovering lignin, US Patent Application No. 20110294991, Dec. 1, 2011) or black liquor filtration (e.g. using ultrafiltration membranes) can be used to generate such lignins.

(27) Table 1 presents the composition of HRC lignin from the LignoForce process compared to LRC lignin from this process. As seen in this table, for example, the ash content of HRC lignin could be as high as 182 the ash content of LRC lignin while the sodium content of HRC lignin could be as high as 169 the sodium content of LRC lignin.

(28) TABLE-US-00001 TABLE 1 Lignin composition HRC softwood LRC softwood kraft kraft lignin lignin Ash, wt % 1.9-30 0.11-1.8 pH 3.8-10.5 2-3.7 Organics, wt % 80-87.1 98.2-99.9 Lignin, wt % 56.4-72.2 90.9-99.9 Acid-insoluble lignin, wt % 49.9-73.6 89.3-97.8 Acid-soluble lignin, wt % 1.17-6.71 1.25-3.88 Na, wt % 0.12-10 0.059-0.9 S, wt % 1.41-2.93 1.46-2.38 Sugars, wt % 0.7-2.92 1.23-2.4 HHV, BTU/lb 6378-9517 10797-11851 C, % 47.3-58.4 65.8-68.1 H, % 4.4-5.9 5.8-6.0 N, % 0.02-0.07 0.03-0.04

(29) In an effort to identify the reasons for which HRC lignins work quite well as an ingredient in wood adhesive compositions, several tests were conducted with HRC and LRC lignins in the wet form. First, the inventors compared the effect of LignoForce HRC and LRC lignin concentration in alkaline solutions composed of 3 wt % and 10 wt % NaOH, on solution pH and viscosity. The results are summarized in FIG. 1.

(30) As shown in FIG. 1, at any given lignin concentration, the pH of the solution prepared with LRC lignin is lower than that of the solution prepared with HRC lignin. This difference in pH can be ascribed to the fact that, in the case of LRC lignin a) no residual alkali are present in the lignin itself and b) all phenolic and carboxylic acid groups are in the acid form. As a result of these two reasons, a higher amount of caustic is required to bring the pH of the resin solution to the targeted pH required for the reaction of phenol, lignin and formaldehyde (which ranges from 9-12) especially if high amounts of lignin are used. In addition, as shown in FIG. 1, solutions of a higher lignin concentration can be prepared when HRC lignin is used, before the viscosity increases dramatically. The same results were obtained in 10 wt % caustic solution (FIG. 2).

(31) Secondly, the inventors compared the effect of lignin concentration in 10 wt % NaOH on solution pH and viscosity in the case of HRC lignins generated from oxidized and unoxidized black liquor. The two solutions were prepared from lignin samples at 63 wt % moisture content. The results obtained are shown in FIG. 3. As shown in this figure, at any given lignin concentration, no major difference is observed in the pH or viscosity of the two lignin solutions. In both cases, more than 35 wt % lignin could be solubilized in 10 wt % NaOH.

(32) Since the pH of lignin solutions in 10 wt % caustic solutions might be too high from the optimum range needed to initiate the reaction of phenol with formaldehyde in the manufacture of phenol formaldehyde (PF) resins (usually prepared at pH values lower than 11), a solution of a lower caustic concentration (3 wt %) was evaluated for solubilizing HRC lignins from oxidized black liquor. As shown in FIG. 4, a 3 wt % caustic solution would be sufficient to prepare lignin solutions containing up to 30 wt % HRC lignin since, at this caustic and lignin dosage levels, the pH of the lignin solution dropped to around 11 and only a small difference was observed in the viscosity of the HRC lignin solution prepared at 3 wt % vs 10 wt % caustic. However, if one is interested in a lignin solution containing more than 30 wt % lignin, a higher concentration of caustic solution would be needed.

(33) In an effort to understand the differences in the solubility and speed of dispersion of HRC vs LRC lignins the inventors analyzed the particle size distribution of both lignins in aqueous solutions. The results are presented in FIG. 5.

(34) Before the measurement, a pestle and mortar was used to grind both HRC and LRC lignins under the same conditions. The size distribution curves of the ground lignin are given in FIG. 5. Although the grinding conditions were identical, both the mean size and size distribution range of the ground HRC lignin were much smaller than those of the LRC lignin. The ground LRC lignin had a size range from about 1 m to about 200 m while the volume weighted mean size, d(vol.), was 16.7 m. In comparison, the HRC lignin was composed of particles ranging from 0.2 m to 1.7 m with a d(vol.) of only 0.7 m. This can be explained based on the following reasons: a) In contrast to LRC lignin, HRC lignin incorporates large amounts of ash in the form of sodium salts or sodium ions associated with phenolic and carboxylic acid groups in the lignin (please see Table 1). The large amount of sodium salts present among the precipitated lignin particles could function as a barrier in terms of preventing them from agglomerating with each other to form larger particles. b) In contrast to LRC lignin, HRC lignin is of high pH. At high pH values, intramolecular and intermolecular hydrogen bonding in lignin is expected to be reduced thereby preventing the lignin particles from agglomerating with each other to from larger particles.

(35) As discussed before, HRC lignin exhibits very different chemical composition and properties from those of LRC lignin. In addition, HRC lignin produced from oxidized black liquor (e.g. via the LignoForce process) exhibits different chemical composition and properties from those of lignin produced from unoxidized black liquor. In an effort to observe the impact of these differences on the performance of these lignins as feedstock materials in the production of lignin-based phenol-formaldehyde (lignin-PF) resins and the application of these resole resins as wood adhesives, these lignins (i.e. HRC and LRC lignins obtained from the LignoForce process (from oxidized black liquor), as well as HRC and LRC lignins obtained from conventional processes (without black liquor oxidation) were used, respectively, in the syntheses of four lignin-based PF resins using the same synthesis procedure and formulation, where the weight ratio between lignin and phenol was kept at 1:2. In order to obtain the same final pH value for each of the lignin-based PF resins, the sodium hydroxide addition rate was adjusted during each resin synthesis according to the alkalinity of each lignin type. The resulting adhesive resins were tested for pH, viscosity, solids content and acid buffer capacity (see Table 2). These resins were also tested for their ability to develop bond strength with wood at three different press temperatures and a fixed press time using the Automatic Bond Evaluation System (ABES), which is a well-known test method in the field of wood adhesives and which is currently being developed to become a standard ASTM test method (see table 3 and FIG. 6).

(36) TABLE-US-00002 TABLE 2 Properties of four lignin-based PF resins Solids Acid Buffer NaOH Viscosity Weight Capacity to pH 10 Weight Lignin-PF pH (cps) (wt %) (meq/g resin solids) (wt %) OLRCL-PF 10.75 211 43.3 0.07 +/ 0.03 8.5 OHRCL-PF 10.55 436 43.7 0.33 +/ 0.08 7.6 ULRCL-PF 10.59 224 44.1 0.07 +/ 0.10 8.5 UHRCL-PF 10.46 340 46.2 0.10 +/ 0.02 7.0 OLRCL-PF: Lignin-based PF resin prepared with LignoForce LRC lignin (lignin obtained from oxidized BL) OHRCL-PF: Lignin-based PF resin prepared with LignoForce HRC lignin (lignin obtained from oxidized BL) ULRCL-PF: Lignin-based PF resin prepared with conventional LRC lignin (lignin obtained from unoxidized BL) UHRCL-PF: Lignin-based PF resin prepared with conventional HRC lignin (lignin obtained from unoxidized BL)

(37) TABLE-US-00003 TABLE 3 Bond strength of four lignin-based PF resins at three press temperatures and a 90 sec press time using ABES (including standard deviations in parenthesis) Press Temperature ULRCL-PF OLRCL-PF UHRCL-P OHRCL-PF ( C.) (MPa) (MPa) (MPa) (MPa) 120 3.17 3.22 3.73 4.10 (0.29) (0.17) (0.19) (0.23) 135 4.70 5.03 5.55 5.77 (0.18) (0.31) (0.56) (0.42) 150 6.98 6.90 6.77 7.20 (0.61) (0.47) (0.70) (0.57)

(38) As can be seen in Table 2, the two lignin-based PF resins made with HRC lignins (produced from oxidized and unoxidized black liquor) appear to have higher acid buffer capacities compared to the two other lignin-based PF resins made of LRC lignins (produced from oxidized and unoxidized black liquor). This was particularly the case for the resin made of HRC lignin produced from oxidized black liquor (e.g. via the LignoForce process), which showed by far the highest acid buffer capacity among the four resins even though all these resins had similar pH values. As described in Chapter 4, page 112 of A. Pizzi's book entitled Advanced Wood Adhesives Technology, a very large portion of the total world output of PF resins is used at very high alkalinity, generally at pH 10-13, which imparts higher reactivity and shorter curing time to the adhesive resins. Conceivably, a high acid buffer capacity allows a phenolic resin to resist changes in pH due to wood acids thereby maintaining a pH and reactivity in the optimum range during the curing process. Therefore, HRC lignins, and, in particular, HRC lignins produced from oxidized black liquor, have certain advantages over LRC lignins in terms of resin reactivity when used as a feedstock for lignin-PF resin manufacturing. This was further substantiated by the ABES test results of shear strength vs. press temperature for the four lignin-based PF resins, as illustrated in Table 3 and FIG. 6. As shown here, the two resins made with HRC lignins (produced from oxidized and unoxidized black liquor) exhibited higher bond strength development than the two resins made with LRC lignins (produced from oxidized and unoxidized black liquor) at lower press temperatures. In particular, the lignin-based PF resin made from HRC lignin derived from oxidized black liquor demonstrated the highest bond strength development. These results provide clear evidence that the use of HRC lignins and, in particular, HRC lignins produced from oxidized black liquor, demonstrate great advantages over LRC lignins in the production of lignin-PF adhesive resins in terms of resin bondability, reactivity and cost.

(39) The preparation of resole lignin-based phenol-formaldehyde (LPF) resins is conducted at alkaline pH values. Hence, if the lignin is in the acid form, as is the case with LRC lignins, large amounts of sodium hydroxide or sodium carbonate need to be used to raise the pH of the reaction medium to the alkaline range (e.g. pH=8-11). As a result of the unique configuration and flexibility of the LignoForce system, the inventors have been able to produce lignins of different residual contents and pH values.

(40) TABLE-US-00004 TABLE 4 Production of lignin of different residual contents and pH values Exp # 1 2 3 4 5 6 7 8 % of H.sub.2SO.sub.4 based 100% 65% 61% 49% 38% 21% 0% 0% on exp #1* (the cake was (without any washed with water wash) water only) Ash, wt % OD 0.60 0.90 1.6 2.2 2.9 3.7 7.0 30 Na, wt % OD 0.050 0.090 0.16 0.21 0.38 0.95 2.7 6.7 S, wt % 1.75 1.80 1.79 1.77 1.91 1.78 1.43 2.01 pH of a 10 wt % 3.23 3.83 4.54 4.96 5.74 7.02 9.28 9.66-11.2 mixture in distilled water (at RT) *normalized to the amount used for the production of LRC lignin

(41) As shown in Table 4 (columns 2-6), by simply changing the acid charge used in the washing step (without any major changes to LignoForce System operation), different lignins having different residual contents (expressed here in the form of ash content) and pH values were produced. In addition to the two common lignins (LRC lignin of an ash content of 0.6 wt % and a pH of 3.23 and HRC lignin of an ash content of 19.53 wt % and a pH of 9.66), the inventors have been able to produce lignins of an ash content ranging from 0.9-3.7 wt % and a pH ranging from 3.83 to 7.02. The inventors refer to this new family of lignins as Medium Residual Content (MRC) lignins. Furthermore, the inventors have, surprisingly, found that LignoForce HRC lignin can be washed with only water, without any major negative impact on filtration rates, providing a lignin with an ash content of 7.02 wt % and a pH of 9.28. These results suggest that by adjusting the amount of wash water added, the inventors can produce lignins with an ash content ranging from 7 to near 30 wt % and a pH from 8 to near 11.2 The inventors refer to this new family of lignins as Water Washed High Residual Content (WWHRC) lignins. Based on the results previously presented in relation to HRC and LRC lignins, the inventors expect MRC and WWHRC lignins to perform at a level intermediate between HRC and LRC lignins with respect to resin bondability, reactivity and cost in the manufacture of lignin-based PF resins. More importantly, the inventors expect such lignins to provide the flexibility needed to use lignin in several other applications at optimum residual content and/or pH for any given application.

(42) One way to incorporate HRC LignoForce and/or other kraft lignins into a glue mix is to make a lignin solution (or suspension) first, and then directly mix such a lignin solution or suspension into the glue mix. Such a lignin solution or suspension can be produced by dissolving (or dispersing) the above-mentioned lignin in an alkaline aqueous solution or water. The HRC lignin content in the solution or suspension should be in the range of 5-50 wt %, preferably from 15 to 40 wt %, further preferably from 20 to 30 wt %.

(43) As seen in Example 1 below, using LRC lignin from a conventional process (a process in which the black liquor was not adequately oxidized) as a replacement of PF resin in plywood glue led to the production of plywood panels with inferior shear strength and wood failure rates. When such lignin was used to replace filler in plywood glue, the shear strength of the plywood panels were comparable with the controls but the wood failure rate was significantly below that of the control and below what would be required by Canadian Standard CSA O151-04 Canadian Softwood Plywood. On the contrary, when HRC LignoForce lignin was used to replace PF resin in plywood glue and/or fillers, both the shear strength and wood failure rates of the test panels produced were as good as or better than the controls (please see Examples 2-5) and well within the limits of Canadian Standard CSA O151-04 Canadian Softwood Plywood.

Example 1

Evaluation of Conventional LRC Lignin as a Replacement of PF Resin in Softwood Plywood Glue Mix

(44) An aqueous solution of 10% NaOH was prepared. The solution was mixed until it became completely homogeneous. The lignin used in this experiment was produced using a conventional process in which the black liquor was not oxidized. Lignin was produced from this 30% solids liquor by: a) Acidifying the black liquor with carbon dioxide to a pH of about 10 to induce the lignin to come out of solution in the form of colloidal particles b) Allowing time for the lignin particles to coagulate to larger particles c) Filtering the lignin suspension to remove the residual black liquor d) Washing the lignin cake with sulphuric acid and water to produce a purified lignin in the acid form (LRC lignin).

(45) Four different mixtures of LRC lignin in 10 wt % NaOH were then prepared. The lignin concentrations were 10, 15, 20 and 25 wt %. The solutions were mixed until complete dispersion of the lignin was accomplished.

(46) After a few hours, the lignin in the 10 wt %, 15 wt % and 20 wt. % lignin solutions was fully dispersed, and the solutions appeared stable. Lignin in the 25 wt. % solution was more difficult to disperse and sediment was always present. After one day, a small deposit appeared at the bottom of container for the 20 wt % solution while the 10 wt % and 15 wt % lignin solutions were still stable. After one week sitting under ambient conditions, the mixtures were filtered through a 14-mesh screen to determine the solubility of the kraft lignin. Our observations are summarized in Table 5. The solutions with 10 wt. % lignin and 15 wt. % lignin were still stable and free of any sediment.

(47) TABLE-US-00005 TABLE 5 Solubility of LRC lignin in 10 wt % sodium hydroxide aqueous solution after one week Lignin in 10% NaOH solution Observations 10% Soluble 15% Soluble 20% Partially soluble 25% Partially soluble

(48) Four glue mixes at the 0 wt %, 20 wt %, 25 wt % and 30 wt % PF replacement levels with LRC lignin were prepared. The composition of these mixtures is shown in Table 6. The viscosity of these mixtures is shown in Table 4. As shown in this table, all of these glue mixes had viscosities suitable for plywood gluing through a roll-spreader (glue applicator).

(49) TABLE-US-00006 TABLE 6 Composition of plywood glue mixtures in which a portion of the PF resin was replaced by LRC lignin PF resin substitution level by LRC lignin* 0 wt % 20 wt % 25 wt % 30 wt % PF resin (44% solids) 114.41 83.54 73.77 65.07 1.sup.st Water 44.49 0.00 0.00 0.00 Wheat flour 13.98 12.76 12.02 11.36 Lignin** 0.00 16.85 19.84 22.50 10% NaOH solution 0.00 95.47 112.40 127.48 PDC filler (corncob) 17.48 15.95 15.03 14.20 Soda ash (sodium carbonate) 6.36 5.80 5.46 5.16 Mix for 30 minutes PF resin (44% solids) 95.34 69.62 61.48 54.23 2.sup.nd Water 7.94 0.00 0.00 0.00 Mix for 5 minutes Total 300.00 300.00 300.00 300.00 Solids (%) 43.37 42.77 41.03 39.49 *Lignin substitution of PF resin was on a solids to solids basis. The ingredients in the recipes were on a weight basis. **Lignin and 10 wt % NaOH solution were pre-mixed before being added to the glue mix. The concentration of lignin in the NaOH solution was 15 wt % (i.e., Lignin:10% NaOH = 15:85 wt./wt.)

(50) TABLE-US-00007 TABLE 7 Viscosity of glue mixes PF resin substitution level by LRC lignin 0 wt % 20 wt % 25 wt % 30 wt % Temperature of glue mix ( C.) 31 28 27 25 Viscosity (cps) immediately after 7280 5220 3330 2510 mixing (before cooling to 25 C.) Viscosity at 25 C. (cps) 8150 5780 3600 2510

(51) A typical softwood plywood glue mix recipe was selected as the control mix and the base model for substitution of the PF component with LRC lignin. Three different levels of PF substitution were tested (20 wt %, 25 wt % and 30 wt % replacement). Each glue mix was formulated to have the same level of total solids and resin/lignin solids. A pre-mix of lignin and 10 wt % NaOH aqueous solution at a wt./wt. ratio of 20:80 was used for the preparation of these glue mixes. In addition, the replacement of the filler component with LRC lignin (in the form of a powder) was also evaluated. The viscosity of the mix increased with lignin content but all mixtures were usable. A total of 50 plywood panels (3-ply, 1212) were produced using thick Douglas-fir veneers, of which 10 panels each were bonded, respectively, with glue mixes in which 0% (control), 20%, 25% and 30% of PF resin was replaced by lignin. In addition, a glue mix was prepared in which 100% of the corn cob filler was replaced with LRC lignin. The plywood panels were manufactured according to the following parameters: Board dimensions: 212 Glue mix loading rate: 30 lb/1000 ft.sup.2 (single glue line) Plywood veneers: thick dry Douglas fir veneers Press platen temperature: 150 C. (302 F.) Press pressure: 200 psi (1.38 MPa) Press time: 240 seconds

(52) The resulting panels were allowed to hot stack for 24 hours before samples were cut in accordance with the CSA standards. Ten test specimens were tested after subjecting them to the vacuum/pressure and boil-dry-boil treatments. The test specimens were cut so that each group of ten would have five samples with open pull and five with closed pull in order that the shear strength might be compared.

(53) The Vacuum/pressure test was performed after treatment in water at 21 C. and a vacuum of 25 inHg for 0.5 hour, followed by 5 atm (75 psi) pressure for 0.5 hour. The resulting samples were then tested for shear strength and % wood failure rate. The boil-dry-boil test was performed after boiling the board samples in water for 4 hours and then drying at 65 C. for 20 hours, followed by boiling in water again for 4 hours. After cooling in cold water, the resulting samples were then tested for shear strength and % wood failure rate.

(54) The average test results of shear strength and % wood failure rate are summarized in Table 8. Based on the data in Table 8, it appears that replacing PF resin with LRC lignin in the glue mixes resulted in reduced bonding strength. Replacing the corn cob filler with LRC lignin powder maintained or somewhat enhanced the shear strength but the wood failure rate was still low. It was also noted that the resulting glue mix was thinner than the control mix.

(55) TABLE-US-00008 TABLE 8 Average test results of shear strength and wood failure (WF) rate Vacuum/Pressure Boil-Dry-Boil Shear WF Shear WF Glue Type (psi) (%) (psi) (%) 0% LRC lignin 183.9 69.7 169.2 78.7 (44.9) (32.9) (48.6) (28.5) 20% LRC lignin 165.8 34.1 135.1 30.8 (49.7) (32.4) (45.3) (31.0) 25% LRC lignin 156.6 18.1 119.3 13.6 (41.1) (24.7) (34.7) (19.1) 30% LRC lignin 146.1 24.2 116.3 33.2 (42.1) (28.4) (39.3) (34.9) 100% of corn cob 211.1 55.8 164.9 38.4 filler replaced with LRC lignin (51.1) (37.5) (35.0) (34.3)

(56) Based on the experimental data obtained, the following observations can be made: 1. The LRC lignin sample was soluble in a 10 wt % sodium hydroxide aqueous solution at the 10 wt % and 15 wt % concentration levels but only partially soluble at the 20 wt % and 25 wt % concentration levels 2. The viscosity of glue mixes at the 20 wt. %, 25 wt. % and 30 wt. % PF resin substitution levels with LRC lignin at 25 C. were 5780, 3600 and 2510 cps, respectively 3. Replacing PF resin with LRC lignin in the glue mixes resulted in reduced plywood bonding strength 4. Replacing the corncob filler with LRC lignin powder maintained or somewhat enhanced the plywood shear strength but the wood failure rate was lower than the control.

Example 2

Substitution of 30 wt % of Commercial Phenol-Formaldehyde (PF) Resin with HRC Softwood LignoForce Lignin in Bonding High-Density Wood (Yellow Birch)

(57) The lignin used in this experiment was produced from 30 wt % solids softwood black liquor using the LignoForce process (Kouisni and Paleologou, U.S. Pat. No. 8,771,464 B2, Jul. 8, 2014) as follows: a) The black liquor was oxidized using oxygen beyond the point at which at least 95% of TRS compounds are oxidized b) The oxidized black liquor of step a) was acidified with carbon dioxide to a pH of about 10 to induce the lignin to come out of solution in the form of colloidal particles c) The lignin slurry of step b) was allowed to stand for about 60 min for the lignin particles to coagulate to larger particles d) The lignin slurry of step c) was filtered using a filter press to remove the residual black liquor to produce HRC lignin at 50-60 wt % solids e) The HRC lignin of step d) was used as needed.

(58) In this investigation, a commercial phenolic resin (coded as ComPF) for plywood application was used. The resin solids content was 45 wt. %, the viscosity 460 cps, and the pH 12.3. HRC lignin in the powder form, as prepared by the LignoForce process as described above, was applied to this phenolic resin to form a 30:70 mixture (coded as HRC30-PF). The adhesive was prepared as illustrated in Table 9.

(59) TABLE-US-00009 TABLE 9 Composition of HRC lignin-based PF resin Solids PF resin Lignin content (Solids, (Solids, Code (%) %) %) pH Remarks ComPF 45 100 12.3 HRC30-PF 45 70 30 12.12 Added water and NaOH to adjust pH to that of the control

(60) Yellow birch veneers (1.5 mm in thickness) were used to make 3-ply plywood panels. The spread rate was 180-190 g/m.sup.2 (36.8-38.8 lb/MSF), the pressure was 305 psi, the press time was 4 minutes, and the temperature was 150 C. For each formulation, 4 panels (dimensions of 300 mm by 110 mm) were made. After the panels were conditioned at 65% RH and 21 C. for two weeks, 32 specimens were cut for each formulation in which 16 specimens were cut for closed pull and 16 specimens were cut for open pull mode.

(61) The specimens were tested after 48 hours of soaking in water. The shear strength is presented in Table 10.

(62) TABLE-US-00010 TABLE 10 Shear strength of 3-ply plywood panels made with PF and lignin PF resins HRC lignin in formulation Shear (Solids/Solids) Strength Code (%) KPa STD HRC30-PF 30 2281 491 ComPF 0 2400 551

(63) After considering the standard deviation (STD) associated with the shear strength values shown in Table 10, the bond strength of the adhesive mix consisting of 30 wt % HRC lignin and 70 wt % commercial liquid PF resin, appears to compare well with that of 100 wt % commercial liquid PF resin.

Example 3

Substitution of 50 wt % of Fillers (Corncob and Superbond) in Softwood Plywood Glue Mix with HRC Softwood LignoForce LigninMill Trial 1

(64) In this mill trial, 50 wt % of fillers (corncob and Superbond) were substituted with softwood LignoForce HRC lignin. This lignin was prepared as discussed in Example 2. In this case, the content of the two fillers in the phenolic glue mix was 6.5 wt. % on a solids basishence, the content of lignin in the phenolic glue mix was 3.25 wt. %.

(65) The HRC lignin was first dissolved in water at a concentration of 17 wt. %, and the lignin solution was mixed in the glue mix at a later stage during the glue mix production process. Douglas fir veneers of thickness were used for plywood production. A total of 70 4 ft8 ft three-ply plywood panels were produced. The panels were hot-stacked before cutting and shipping to the lab for testing. The parameters for plywood production in the mill trial are summarized in Table 11.

(66) TABLE-US-00011 TABLE 11 Parameters for plywood production in the first mill trial Glue mixer Filler replacement level by HRC lignin 50% Total mixed weight 800 lbs (363 kg) Mixed glue viscosity 750 cps at 90 F. (750 mPa .Math. s at 32.2 C.) Mixed glue temperature 82 F. (27.8 C.) Lay-up line Ambient temperature 70 F. (21.1 C.) Average veneer temperature 75-100 F. (23.9-37.8 C.) Glue spread rate 60 lbs/MDGL (293.2 g/m.sup.2) Open assembly time (1.sup.st glue line to pre- 9 min 40 sec press) Closed assembly time (1.sup.st glue line to 13 min hot press close) Total assembly time (1.sup.st glue line to hot 16 min 45 sec press open) Press Pre-press time 3 min Hot press time 4 min (2 panels/opening) Hot press temperature 315 F. (157.2 C.) Inner glue line temperature 213 F. (100.6 C.) Hot press pressure About 190 psi (1.31 MPa)

(67) The bonding performance of plywood panels was evaluated according to the Canadian Standard CSA O151-04 Canadian Softwood Plywood. Twenty panels were randomly selected from the 70 test panels for this evaluation. Ten specimens were cut from each of the 20 selected test panels and the 20 control panels. Five of the specimens marked with odd numbers were tested after subjecting them to the vacuum-pressure (VP) cycle treatment and the other five marked with even numbers were tested after subjecting them to the boil-dry-boil (BDB) cycle treatment.

(68) The glue mix produced with 50 wt % lignin substitution for fillers appeared to be quite homogeneous and free-flowing without any lumps or aggregates. The experimental glue mix was transferred into a storage tank without any abnormal residue left in the mixer. The viscosity of the glue mix was 750 cps at 90 F., which was lower than the viscosity of the control (targeted viscosity: 1250-1400 cps) normally used in mill production. However, it was still suitable for glue spreader application and other glue applicators, such as glue spray line. The glue mix was applied to the veneers using a glue spreader and the production process went smoothly without any problems with respect to processability or distribution of the glue on the veneers.

(69) A sample of the experimental glue mix was stored at room temperature for an extended period of time. No separation, precipitation, or glue skin was observed after the experimental glue mix was stored for 5 days. The viscosity was 1020 cps at 25 C. (77 F.) after 5 days of storage, suggesting that the glue mix was stable.

(70) TABLE-US-00012 TABLE 12 Shear test results of plywood panels from the first mill trial Shear % Panels % Panels Strength Wood Failure passing 60% passing 30% Filler (psi) (%) WF rate WF rate Vacuum-pressure cycle Control 200 (17) 87 (6) 100 100 50% filler 207 (16) 86 (4) 100 100 substitution by HRC lignin Boil-dry-boil cycle Control 196 (21) 89 (4) 100 100 50% filler 197 (19) 86 (7) 100 100 substitution by HRC lignin

(71) The bond performance of both the experimental and control panels were evaluated and the test results are summarized in Table 12. As seen in this table, the shear strength of the test panels in which 50 wt % of fillers were replaced with LignoForce HRC lignin in the plywood glue compare well with the control panels following either the vacuum-pressure cycle or the boil-dry-boil cycle treatments. In addition, the average wood failure rates for both the control and the test panels surpassed the 60% level after either the vacuum-pressure cycle or the boil-dry-boil cycle treatments. In fact, all of the control and test panels surpassed the 80% wood failure rate either after the vacuum-pressure treatment or after the boil-dry-boil treatment. Therefore, both the control and the test panels met the bond requirements according to the Canadian standard.

Example 4

Substitution of 10 wt % of Phenol Formaldehyde (PF) Resin with Softwood LignoForce HRC Lignin in Plywood Glue MixMill Trial 2

(72) This example shows that 10 wt % of phenolic resin in softwood plywood phenolic glue mix formulations can be substituted with LignoForce HRC lignin. The content of phenolic resin (solids basis) in the control phenolic glue mix was 30.2 wt. %, which means that the content of lignin was about 3.0 wt %.

(73) The lignin was first dissolved in an alkaline aqueous solution at a total solids content of 28 wt. %, and the lignin solution was blended into the glue mix at a later stage during the glue mix production process. Spruce veneers of thickness were used for plywood production. About 5000 lbs of phenolic glue mix was produced and used to manufacture 3-ply plywood panels. Forty panels were randomly selected from the manufactured plywood products for bond quality testing. The forty control panels, which were manufactured under the same conditions, were tested for comparison purposes. The main parameters for plywood production in the mill trial are summarized in Table 13. The bonding performance of plywood was evaluated according to the Canadian Standard CSA O151-04 Canadian softwood plywood, as described in Example 2.

(74) TABLE-US-00013 TABLE 13 Major parameters for plywood production in the second mill trial Veneer thick spruce Panel size and type 48 96, 3-ply Glue spread rate 27 lbs/MSGL (131.9 g/m.sup.2) Total assembly time Ranged from 10 min to 24 min Press pressure About 190 psi (1.31 MPa) Press temperature 138 C. (280 F.) Press time 5 min (2 panels/opening) Total glue mix About 5000 lbs

(75) The phenolic glue mix produced was visually examined and looked very smooth without any unacceptable lumps and aggregates. The viscosity was in the required range for glue application in the plywood mill. The glue mix appeared to spread uniformly and smoothly on the veneers and all the glue mix made was successfully used up in plywood production.

(76) The bond performance of the plywood panels bonded with the test phenolic glue mix and the control was evaluated accordingly. The shear results are listed in Table 14. As seen in this table, the shear strength of the test panels in which 10 wt % of PF resin was replaced with LignoForce HRC lignin in the plywood glue compares well with that of the control panels following either the vacuum-pressure cycle treatment or the boil-dry-boil cycle treatment. In addition, the average wood failure rate surpassed 80% (industry standard requirement) for both the control and test panels after the samples were subjected to either the vacuum-pressure cycle or the boil-dry-boil cycle treatments. These results clearly demonstrate the technical feasibility of replacing 10 wt. % of phenolic resin with softwood LignoForce HRC lignin in phenolic glue mixes used in exterior-grade softwood plywood manufacturing.

(77) TABLE-US-00014 TABLE 14 Shear test results of plywood panels from the second mill trial Shear Strength Wood Failure Rate Glue Mix (psi) (%) Vacuum-pressure cycle Control 175 (26) 90 (17) 10 wt % PF substitution with 170 (28) 83 (25) HRC lignin Boil-dry-boil cycle Control 170 (34) 88 (21) 10 wt % PF substitution with 166 (28) 80 (26) HRC lignin

Example 5

Substitution of 20 wt % of Phenol-Formaldehyde Resin and 20 wt % of all Additives in Plywood Glue Mix Using Softwood LignoForce HRC LigninMill Trial 3

(78) This example shows that 20 wt % of phenolic resin and 20 wt % of all additives in the phenolic glue mix formulation can be substituted with softwood LignoForce HRC lignin. The content of phenolic resin (solids basis) in the control phenolic glue mix was 30.2 wt. %, and the additive content was 12.2 wt %. Therefore, the lignin content in the glue mix was about 8.4 wt %.

(79) TABLE-US-00015 TABLE 15 Major parameters for plywood production in the third mill trial Veneer thick spruce Panel size and type 48 96, 3-ply Glue spread rate 25 lbs/MSGL (122.2 g/m.sup.2) Total assembly time Ranged from 10 min to 24 min Press pressure About 190 psi (1.31 MPa) Press temperature 138 C. (280 F.) Press time 5 min (2 panels/opening) Total glue mix About 5000 lbs

(80) The lignin was first dissolved in an alkaline aqueous solution at a total solids content of 28 wt. %, and the lignin solution was blended into the glue mix at a later stage during the glue mix production. Spruce veneers of thickness were used for plywood production. About 5000 lbs of phenolic glue mix was produced and used to manufacture 3-ply plywood panels. Twenty panels were randomly selected from the manufactured plywood products for bond quality testing. The twenty control panels, which were manufactured under the same conditions, were tested for comparison purposes. The main parameters for plywood production in the mill trial are summarized in Table 15. The bonding performance of plywood was evaluated according to the Canadian Standard CSA O151-04 Canadian Softwood Plywood.

(81) The lignin glue mix produced looked very homogeneous without any unacceptable lumps that might lead to non-uniform glue application on the veneers. The viscosity of the lignin glue mix was lower than that of the control glue mix, but it was suitable for application with the glue applicator at the mill. All the glue mix produced was successfully used in manufacturing three-ply softwood plywood panels.

(82) TABLE-US-00016 TABLE 16 Shear test results of plywood panels from the third mill trial Shear Wood Strength Failure Rate Glue mix (psi) (%) Vacuum-pressure cycle Control 163 (26) 81 (28) Substitution of 20 wt % PF and 20 wt % 154 (45) 83 (26) of all additives with HRC lignin Boil-dry-boil cycle Control 148 (39) 80 (31) Substitution of 20 wt % PF and 20 wt % 146 (35) 84 (25) of all additives with HRC lignin

(83) The bond performance of the plywood panels bonded with the lignin-based glue mix and the control was evaluated and the results are shown in Table 16. As shown in this table, the average wood failure rates surpassed 80% (industry standard requirement) for the test panels after the samples were subjected to either the vacuum-pressure cycle or the boil-dry-boil cycle treatment. Both the shear strength and wood failure rate of the test panels were comparable to those of the control. These results clearly demonstrated the technical feasibility of replacing 20 wt. % of phenolic resin and 20 wt % of fillers with softwood LignoForce HRC lignin in phenolic glue mixes used in exterior-grade softwood plywood manufacturing.

Example 6

Substitution of 10 wt % of PF Resin and 100 wt % of Additives in Plywood Glue Mix with Softwood LignoForce HRC Lignin

(84) This example shows that 10 wt % of PF resin and 100 wt % of all additives in the phenolic glue mix formulation can be substituted with softwood LignoForce HRC lignin in plywood glue mixes. The content of PF resin (solids basis) in the control phenolic glue mix was 30.2 wt %, and the additive content was 12.2 wt %. Therefore, the lignin content in the glue mix was about 15.2%. The HRC lignin was first mixed in an alkaline aqueous solution, and the resulting lignin solution was blended with a commercial PF resin prior to plywood panel production. Spruce veneers of thickness were used for plywood production. The control panels were also manufactured under the same conditions. The main parameters for plywood production in the pilot plant are summarized in Table 17.

(85) TABLE-US-00017 TABLE 17 Major parameters for plywood production in the pilot plant Veneer thick spruce Panel size and type 15 15, 3-ply Glue spread rate 30 lbs/MSGL (146.6 g/m.sup.2) Total assembly time 20 min Press pressure About 200 psi (1.38 MPa) Press temperature 150 C. Press time 4 min Panel replicates 3

(86) The bonding performance of plywood was evaluated according to the Canadian standard CSA O151-04 Canadian Softwood Plywood. Thirty-two specimens were cut from each test panel and control panel. Sixteen of the specimens were tested after the vacuum-pressure cycle treatment and the other sixteen were tested after the boil-dry-boil cycle treatment. The lignin glue mix looked homogeneous and the viscosity was comparable to that of the control. The bonding performance of the panels was evaluated and the shear test results are listed in Table 18. As can be seen in this table, the wood failure rate of the test panels significantly surpassed 80%. Both the shear strength and wood failure rate of the test panels were comparable to or even better than those of the control panels. These results clearly demonstrated the technical feasibility of replacing 10 wt. % of phenolic resin and 100 wt % of all fillers with softwood LignoForce HRC lignin in phenolic glue mixes used in exterior-grade plywood manufacturing.

(87) TABLE-US-00018 TABLE 18 Shear test results of softwood plywood panels manufactured in the pilot plant Shear Wood Strength Failure Rate Glue mix (psi) (%) Vacuum-pressure cycle Control 123 (42) 85 (15) Substitution of 10 wt % of PF and 130 (52) 91 (9) 100 wt % of additives with HRC lignin Boil-dry-boil cycle Control 116 (45) 91 (10) Substitution of 10 wt % of PF and 111 (47) 92 (7) 100% of additives with HRC lignin

Example 7

Preparation of Lignin-Based PF Resins for OSB Manufacture Through the in-Situ Polymerization of Softwood LignoForce HRC Lignin with Phenol, Formaldehyde and Sodium Hydroxide or by the Post-Addition of LignoForce HRC Lignin to PF Resin or Lignin-Based PF Resin

(88) Two lignin-based phenol formaldehyde resins (HRC lignin-PF I and HRC lignin-PF II) were synthesized in the lab using softwood LignoForce HRC lignin as a partial replacement of phenol in the PF resin making process. The ratio of HRC lignin to phenol was 0.55:1 and 1:1 (solids to solids weight ratio). The molar ratio of formaldehyde to phenol was adjusted to be between 2.1 and 2.4, the solids content of the resins was about 45 wt %, the viscosity was targeted to be 150-200 cps, and the final pH was around 10.5. The resin composition and loading of the PF resin controls and the lignin-based PF resins is shown in Table 19. Table 19 also shows the composition of three additional resin formulations that were prepared through the post-addition of HRC lignin to the lab-made PF resin (No. 5) as well as the post-addition of HRC lignin to lignin-based PF resins Nos. 2 and 3. The OSB panel manufacturing parameters are shown in Table 20.

(89) TABLE-US-00019 TABLE 19 Resin composition and loading Lignin in Loading Resin (S/S) Core Loading No. Face Resin Form (% wt.) (% wt.) Resin (%) 1 Lab PF Liquid 3.0 0 Com 3 powder PF 2 HRC lignin- Liquid 3.0 20.6 Com 3 PF I powder PF 3 HRC lignin- Liquid 3.0 32.1 Com 3 PF II powder PF 4 Com Liquid Liquid 3.0 0 Com 3 PF powder PF 5 lab PF + HRC Liquid 2.5/0.5 16.7 Com 3 lignin powder PF 6 Lignin PF I + Liquid 2.5/0.5 33.8 Com 3 HRL lignin powder PF 7 Lignin PF II + Liquid 2.5/0.5 43.4 Com 3 HRC lignin powder PF Post-added HRC lignin was dissolved in water at the 15 wt % solids level and added to the PF resin at the lignin in resin solids levels indicated in the above table (items 5-7)

(90) TABLE-US-00020 TABLE 20 OSB panel manufacturing parameters Terms Contents Panel dimensions 11.1 mm ( 7/16 in) 610 mm (24 in) 610 mm (24 in) Panel construction Random orientation/three layer Mass distribution 25/50/25 Wood species 100% Aspen Supports Wax paper at the bottom Wax paper on the top The thickness was controlled by the position of the platen Target mat MC Face: 6.5-7.5%; Core: 3.5-4.0% Slack wax content 0.5 wt % Air pressure for 30 psi wax application Resin in face 3 wt % or 4 wt % PF or lignin PF (phenolic resin made in-house) (with/without lignin (solid basis) Resin in core 3 wt % commercial PF powder resin Blender Air sprayed system Blender rotation speed 11 rpm Liquid resin feeding rate Standard Dwell time Standard for both liquid and powder Target density (OD basis) 39 0.5 lb/ft.sup.3 (624 24 kg/m.sup.3) Press temperature 220 C. (428 F.) (surface of platen) Total press time 150 seconds (daylight to daylight) Close time 30 seconds Degas 30 seconds Replicate 2

(91) After pressing and prior to testing, all panels were conditioned in a chamber at 65% RH/20 C. for two weeks to reach the equilibrium moisture content. Internal bond (IB) strength, modulus of rupture (MOR), modulus of elasticity (MOE), 24-h thickness swelling (TS) and 24-h water absorption (WA) of the panels were tested according to ASTM D 1037-12.

(92) The average values of IB of the OSB panels made from phenolic resin with/without lignin in the face layer are listed in Table 21.

(93) TABLE-US-00021 TABLE 21 IB of OSB panels made with/without HRC lignin incorporated in phenolic resin IB Density No. MPa STD kg/m.sup.3 STD 1 0.27 0.04 608 18 2 0.31 0.06 616 18 3 0.31 0.04 616 16 4 0.30 0.04 607 25 5 0.32 0.04 608 14 6 0.32 0.04 608 14 7 0.32 0.04 614 18 STD: standard deviation

(94) In the case of all specimens listed in Table 21, during testing, the failure occurred in the core. This suggested that, in all cases, the face resin was fully cured and had sufficient strength to support the specimens during the testing. As seen in Table 21, all panels had IB comparable to the two control OSB panels made from commercial PF (No. 4) and lab PF (No. 1) resins. The OSB panel made with lignin-based PF resin with HRC lignin added to it to bring the total resin lignin content to the 43.4 wt % level (No. 7) (based on total resin dry solids), also had an IB (0.32 MPa) comparable to the two controls.

(95) The average TS and WA of all OSB panels is presented in the Table 22.

(96) TABLE-US-00022 TABLE 22 TS & WA of OSB panels made with/without lignin incorporated in the phenolic resin Density TS WA No. kg/m.sup.3 % STD % STD 1 606.6 17.9 24.1 1.3 45.6 1.4 2 598.0 19.3 26.9 0.6 48.6 1.4 3 614.6 8.1 26.4 1.7 49.2 2.2 4 624.9 28.4 27.1 1.2 45.8 1.4 5 637.0 24.4 26.8 1.5 44.2 1.7 5 628.6 20.3 27.2 1.6 44.9 0.6 6 631.3 26.4 27.8 2.0 47.9 4.3 7 618.6 8.4 28.9 2.9 48.1 1.8

(97) Except for the control OSB panels (No. 1) for which the PF resin was made in the lab, the others had thickness swelling comparable with the OSB panels made with the commercial PF resin control. For water absorption, all OSB panels had relatively similar values ranging from 44.2% to 49.2%.

(98) After reaching an equilibrium in the moisture content at 65% RH and 21 C. over a period of 3 weeks, the OSB panel specimens were tested under dry conditions. The average values of the different formulations are shown in Table 23.

(99) TABLE-US-00023 TABLE 23 Dry flexural properties of OSB panels made with/without lignin incorporated in phenolic resin Density MOR MOE No. kg/m.sup.3 STD MPa STD MPa STD 1 626.8 33.2 25.01 5.61 3540 484 2 629.1 17.3 29.33 4.70 3914 452 3 619.8 22.2 26.76 3.03 3709 475 4 622.1 27.0 25.90 2.69 3745 507 5 637.1 43.9 30.41 6.43 3857 528 6 638.7 27.1 29.73 8.04 4024 842 7 624.7 24.7 27.07 6.56 3511 496

(100) As can be seen in Table 23, addition of HRC lignin into lab-cooked PF or lab-cooked lignin-based PF resins does not have a negative impact on the bending strength and the modulus. These results clearly demonstrated the technical feasibility of replacing 16.7-43.4 wt % of phenolic resin with softwood LignoForce HRCL in phenolic resin formulations used as an adhesive in OSB manufacturing.

Example 8

Post-Addition of Softwood LignoForce HRC Lignin to Phenol Formaldehyde Resin for OSB Applications

(101) Phenol-formaldehyde (PF) resin was synthesized in the lab using a molar ratio of formaldehyde to phenol between 1.8 and 2.1. The solids content of the resin was about 48 wt. %, the viscosity was targeted to be 1500-2500 cps and the final pH was around 10. This PF resin was divided into 6 portions. For each portion, urea and/or lignin was added to make the formulations listed in Table 24. For lignin and urea, 50 wt. % mixtures were prepared for the purpose of this investigation.

(102) TABLE-US-00024 TABLE 24 Formulations of phenolic resin with/without HRC lignin & urea Initial (% wt.) No. PF Lignin.sup.1 Urea.sup.2 PF resin without lignin 1 100 0 30 2 100 0 50 PF resin with addition of 20 wt % HRC lignin 3 80 20 30 4 80 20 50 PF resin with addition of 30 wt % HRC lignin 5 70 30 30 6 70 30 50 .sup.1based on PF resin solids; .sup.2based on PF resin solids plus lignin solids

(103) A Brookfield viscometer from Brookfield Engineering Laboratories, Inc. (Middleboro, Mass., USA, 02346) and a small sample adapter also from Brookfield were used to monitor the viscosity at 25 C. At various time intervals, a 10-15 mL sample was taken out and cooled down, then placed in a water bath at 25 C. for a certain amount of time before being transferred to the small adapter of the Brookfield viscometer for the measurement of viscosity.

(104) TABLE-US-00025 TABLE 25 Viscosity of different resin formulations Initial (% wt.) Viscosity No. PF Lignin.sup.1 Urea.sup.2 (cps) PF resin without lignin 1 100 0 30 174 2 100 0 50 64 PF resin with addition of 20 wt % HRC lignin 3 80 20 30 450 4 80 20 50 124 PF resin with addition of 30 wt % HRC lignin 5 70 30 30 1040 6 70 30 50 188 7 (com PF) 100 0 0 .sup.1based on PF resin solids; .sup.2based on PF resin solids plus lignin solids

(105) As seen in Table 25, urea addition and the ratio of urea to lignin have a significant impact on viscosity. With the addition of 30 wt. % lignin in the resin, the viscosity of the mixture of PF plus lignin is quite high. After adding urea at the 50 wt. % level, the viscosity is reduced significantly.

(106) A series of OSB panels were made with the different resin formulations as shown in Table 26. The OSB manufacturing parameters are shown in Table 27.

(107) TABLE-US-00026 TABLE 26 Composition and loading of resin formulations used to make OSB panels Face Layer Core Layer Loading Loading No. Face Resin* Form (wt %) Core Resin (wt %) 1 No. 1 Liquid 3 Commercial 3 powder PF 2 No. 2 Liquid 3 Commercial 3 powder PF 3 No. 3 Liquid 3 Commercial 3 powder PF 4 No. 4 Liquid 3 Commercial 3 powder PF 5 No. 5 Liquid 3 Commercial 3 power PF 6 No. 6 Liquid 3 Commercial 3 powder PF 7 Com. PF Liquid 3 Commercial 3 powder PF *The resin codes are indicated in the previous table

(108) TABLE-US-00027 TABLE 27 OSB panel manufacturing parameters with lignin Panel dimensions 11.1 mm ( 7/16 in) 610 mm (24 in) 610 mm (24 in) Panel construction Random orientation/three layer Mass distribution 25/50/25 Wood species 100% Aspen Supports Waxed paper at the bottom, no caul plate No Frame on the top The thickness is control by position of platen Target mat MC Face: 6.5-7.5%; Core: 3.5-4.0% Slack wax content 0.5% Air pressure for 30 psi (206.8 kPa) wax application Resin in face 3 wt % PF (phenolic resin made in-house) (with/without lignin plus urea (solid basis) Resin in core 3 wt % commercial PF powder resin Blender Air sprayed system Blender rotation speed 11 rpm Liquid resin feeding rate Standard Dwell time Standard for both liquid and powder Target density (OD basis) 39 0.5 lb/ft.sup.3 (624 24 kg/m.sup.3) Press temperature 220 C. (428 F.)(surface of platen) Total press time 150 seconds (daylight to daylight) Close time 30 seconds Degas 30 seconds Replicate 2

(109) After pressing and prior to testing, all panels were conditioned in a chamber at 65% RH at 20 C. for several days. Internal bond (IB) strength, modulus of rupture (MOR), modulus of elasticity (MOE), 24-h thickness swelling (TS) and 24-h water absorption (WA) of the panels were tested according to ASTM D 1037-12. The vertical density profile (VDP) of each panel after conditioning was measured by an X-ray (QDP-01X Density Profile) system from 50-mm50-mm specimens, which were also used for measuring IB strength afterwards. As mentioned before, to investigate the impact of post-addition (via post-blending) of HRC lignin and urea on the phenolic resin performance, several formulations were prepared in which either 30 wt. % or 50 wt. % urea was added to the phenolic resins containing 20 wt. % or 30 wt. % HRC lignin. The solids contents of the various formulations are illustrated in Table 28.

(110) TABLE-US-00028 TABLE 28 Solids content of the various components in resin formulations Ratio of components Dry solids content expressed based on a liquid (wt. Resin on a % dry solids basis %) basis Formulation PF lignin urea PF Lignin urea Total 1 76.9 0.0 23.1 37.3 0.0 11.2 48.4 2 66.7 0.0 33.3 32.4 0.0 16.2 48.6 3 61.5 15.4 23.1 30.0 7.5 11.3 48.8 4 53.3 13.3 33.3 26.1 6.5 16.3 48.9 5 53.8 23.1 23.1 26.3 11.3 11.3 48.9 6 46.7 20.0 33.3 22.9 9.8 16.3 49.0 7 100 0 0 48.0 0 0 48.0

(111) As can be seen in Table 28, the addition of lignin and urea into a PF resin formulation can dramatically reduce the PF resin content in the formulation thereby leading to significant cost savings given that both HRC lignin and urea are less expensive than PF resins. For example, in resin formulation No. 6, the resin contains less than 50 wt. % PF resin (46.7 wt. %) in the formulation.

(112) The internal bonding strength (IB) of OSB samples made with the different formulations is listed in Table 29.

(113) TABLE-US-00029 TABLE 29 Internal bonding (IB) of OSB made with different resin formulations Density IB adj IB* Code kg/m.sup.3 Mpa Mpa 1 662 14 0.565 0.058 0.546 0.052 2 661 29 0.488 0.065 0.474 0.073 3 657 11 0.552 0.057 0.537 0.049 4 674 23 0.531 0.068 0.507 0.064 5 661 19 0.532 0.058 0.515 0.053 6 656 16 0.484 0.075 0.472 0.076 Com PF 637 22 0.517 0.076 0.512 0.059 *Adj. IB: adjusted IB to 640 kg/m3 by IB (640/density)

(114) After considering the standard deviation of the samples tested, there are no significant differences among the different formulations even though the addition of 50 wt. % urea in any given formulation (e.g. formulations 2, 4 and 6) appears to lead to a lower IB compared to less urea in the formulation (e.g. formulations 1, 3 and 5).

(115) The thickness swelling (TS) and water absorption (WA) of OSB panels made with the different formulations of this example are presented in Table 30.

(116) TABLE-US-00030 TABLE 30 TS & WA of OSB made with different resin formulations Density TS WA Code kg/m.sup.3 % % 1 636 26 22.4 2.1 42.9 3.6 2 641 30 22.3 1.8 43.7 3.6 3 650 34 25.5 2.7 44.1 3.7 4 648 24 25.6 2.3 45.9 2.1 5 635 39 24.3 3.0 46.3 5.2 6 645 20 24.1 2.6 41.6 1.9 Com PF 638 30 25.3 1.6 47.5 3.6

(117) As shown in Table 30, in the case of resin formulations incorporating HFC lignin, the average values for thickness swelling are of the same order of magnitude as those of the controls.

(118) The bending strength (MOR) and bending modulus (MOE) of OSB panels made with different formulations and tested under dry conditions are shown in Table 31.

(119) TABLE-US-00031 TABLE 31 MOE & MOR of OSB made with different resin formulations (dry condition) adjusted adjusted Density MOE MOR MOE* MOR* Code Kg/m.sup.3 MPa MPa MPa MPa 1 632 5223 382 39.11 5.03 5288 264 39.48 3.19 2 642 5073 059 35.48 7.09 5067 1115 35.43 7.44 3 632 4830 756 32.42 9.59 4886 725 32.77 9.43 4 621 4928 423 34.33 5.08 5076 432 35.37 5.28 5 629 4970 315 36.98 5.36 5060 279 37.62 5.01 6 624 4633 419 29.57 3.23 4744 311 30.34 3.49 Com PF 659 4706 180 32.29 4.37 4580 321 31.45 4.82 (640/density); adjusted MOR = MOR (640/density)

(120) As seen in Table 31, at the 30 wt. % urea addition level, post-addition of lignin into PF resins does not significantly reduce the strength (MOR) and the modulus (MOE). However, at the 50 wt % urea addition level, there is some reduction in strength. The bending strength (MOR) and bending modulus (MOE) of OSB panels made with different formulations and tested under wet conditions are listed in Table 32.

(121) TABLE-US-00032 TABLE 32 MOE & MOR of OSB made with different formulations (wet condition) Density MOE MOR adj MOE* adj MOR* Code Kg/m.sup.3 MPa MPa MPa MPa 1 650 2807 489 18.07 4.42 2754 384 17.73 4.08 2 636 2310 361 16.03 3.24 2332 398 16.21 3.63 3 627 2428 526 15.81 3.07 2468 465 16.10 2.82 4 642 2344 298 16.20 2.72 2331 225 16.13 2.57 5 640 2186 226 15.01 4.84 2183 181 14.93 4.56 6 644 2454 273 15.48 2.55 2437 256 15.38 2.55 Com PF 654 2676 269 19.31 1.98 2618 236 18.89 1.71 (640/density); adjusted MOR = MOR (640/density)

(122) As seen in Table 32, under wet conditions, at the 50 wt. % urea addition level (formulations 2 and 4), the MOE and MOR are somewhat lower than what was obtained with the commercial resin control and/or formulations in which urea was used at the 30 wt % urea addition level.

(123) The above results demonstrated that post-addition of softwood LignoForce HRC lignin into phenolic resins increases the viscosity of the resin systemthe higher the lignin content, the higher is the viscosity. However, the incorporation of urea into the resin system reduces the viscositythe higher the urea charge the lower the viscosity. The above results also showed that by adding urea to PF resin formulations, it becomes possible to partially replace PF resin with softwood LignoForce HRC lignin at the 22-30 wt. % replacement level (based on resin solids) without any significant decrease in the mechanical and physical properties of 3-layer sandwich OSB panels such as IB, TS & WA and MOE & MOR. These results show that post-addition of LignoForce HRC lignin to PF resins for use as an adhesive in OSB manufacturing is a technically feasible and cost-effective option.