ADHESIVE COMPOSITION COMPRISING HEAT TREATED DRY PLANT MEAL AND A WATER SOLUBLE PREPOLYMER AND/OR WATER SOLUBLE REACTIVE PREPOLYMER

Abstract

The invention relates to a process for preparing an adhesive composition comprising a heat treated dry plant meal, said heat treated dry plant meal and relating dispersions, adhesive compositions, articles and uses of said heat treated dry plant meal.

Claims

1. A process for preparing an adhesive composition comprising the steps of: providing a heat treated dry plant meal which is capable of reducing the viscosity of a dispersion in water of said heat treated dry plant meal compared to the same dispersion in water of the non heat treated dry plant meal, and mixing the heat treated dry plant meal with water and a water soluble prepolymer and/or a water soluble reactive prepolymer to provide an adhesive composition.

2. A process for preparing an adhesive composition comprising the steps of: providing a dry plant meal heat treated at a temperature of at least 100° C., and mixing the heat treated dry plant meal with water and a water soluble prepolymer and/or a water soluble reactive prepolymer to provide an adhesive composition.

3. The process according to claim 1, wherein the temperature of the heat treatment is at least 115° C.

4. The process according to claim 1, wherein the dry plant meal comprises at least 15 wt % of proteins, on the total weight of the dry plant meal.

5. The process according to claim 1, wherein the dry plant meal has a granulometry d50 of at least 20 μm.

6. The process according to claim 1, wherein the dry plant meal is submitted to a heat treatment during at least 5 minutes.

7. A process for preparing an article with the adhesive composition prepared according to claim 1, comprising a step of contacting the adhesive composition with a lignocellulosic material to provide lignocellulosic material impregnated with the adhesive composition.

8. An adhesive composition comprising a heat treated dry plant meal, water and a water soluble prepolymer and/or a water soluble reactive prepolymer.

9. The adhesive composition according to claim 8, the adhesive composition having a viscosity at 20° C. of less than 1000 mPa.Math.s.

10. The adhesive composition according to claim 8, the adhesive composition being sprayable.

11. (canceled)

12. (canceled)

13. The process according to claim 1, wherein the temperature of the heat treatment is at least 135° C.

14. The process according to claim 1, wherein the temperature of the heat treatment is at least 150° C.

15. The adhesive composition according to claim 8, the adhesive composition having a viscosity at 20° C. of less than 500 mPa.Math.s.

Description

[0174] The invention will be better understood in the light of the following examples, given by way of illustration, with reference to:

[0175] FIG. 1 that is a scale for evaluating the visual aspect of a dispersion of a plant meal and water;

[0176] FIG. 2 that is a diagram illustrating the viscosity of dispersions prepared from water and ground rapeseed meal subjected to different thermal treatments, depending on the solid content of the dispersions expressed in weight percentage (% dispersion);

[0177] FIG. 3 that is a diagram illustrating the viscosity of dispersions at a solid content of 23 wt % prepared from water and ground rapeseed meal of two different origins (GCXX-12/18 or LMXX-26/18) subjected or not to a thermal treatment, depending on the granulometry d(50);

[0178] FIG. 4 that is a diagram illustrating the viscosity of dispersions prepared at a laboratory scale from water and ground rapeseed meal of two different origins (GCXX-12/18 or LMXX-26/18) subjected or not to a thermal treatment and having a granulometry d(50) of 30 μm, depending on the solid content of the dispersions;

[0179] FIG. 5 that shows pictures of dispersions prepared from water and non-treated rapeseed meal after 4 days (left picture), and from water and heat-treated rapeseed meal after 7 days (right picture);

[0180] FIG. 6 that is a diagram illustrating the concentration of microorganisms per mL of a dispersion at a solid content of 20 wt % prepared from water and heat treated rapeseed meal, depending on the days after dispersing;

[0181] FIG. 7 that is a diagram illustrating the viscosity of dispersions prepared from water and ground rapeseed meal (heat treated or not), depending on the solid content of the dispersions;

[0182] FIG. 8 that is a diagram illustrating the viscosity of dispersions prepared at a pilot scale from water and ground rapeseed meal (optionally heat treated before grinding), depending on the solid content of the dispersions;

[0183] FIG. 9 that is a diagram illustrating the viscosity of dispersions at a solid content of 20 wt % prepared from water and ground sunflower meal (heat treated or not), depending on the pH of the dispersions;

[0184] FIG. 10 that is a diagram illustrating the viscosity of dispersions at a solid content of 30 wt % prepared from water and ground rapeseed meal (heat treated or not), depending on the pH of the dispersions;

[0185] FIG. 11 that is a diagram illustrating the internal bonding (IB) of particle boards made from adhesive compositions comprising untreated or heat treated ground plant material of different origin;

[0186] FIG. 12 that is a diagram illustrating the thickness swelling (TS) of particle boards made from adhesive compositions comprising untreated or heat treated ground plant material of different origin;

[0187] FIG. 13 that is a diagram illustrating the relative strength development of adhesive compositions (Formulas 5A, 5B, 6A and 6B) depending on the press time;

[0188] FIG. 14 that is a diagram illustrating the relative strength development of adhesive compositions (Formulas 1, 2, 3 and 4) depending on the press time;

[0189] FIG. 15 that is a scheme of a sterilization reactor.

EXAMPLE 1

Materials and Methods

[0190] Materials

[0191] All raw material used are listed in Table 1.

TABLE-US-00001 TABLE 1 description of the raw material used in the Examples, the percentages being weight percentages Unless otherwise specified, the meal is in loose (powder) form. Protein Oil Name content content Supplier Manufacturing process Wheat draff 27% 6.4% Aso By-product from the manufacture of Nutrition alcohol by distillation from wheat Corn draff 21% 13.9% Aso By-product from the manufacture of Nutrition alcohol by distillation from corn Linseed meal 34% n.d. Saipol From crushing process of flaxseed Soy meal 51% 0.7% ADM From crushing process of soy seeds extracted with hexane Sunflower meal 37% 1.3% Saipol From crushing process of sunflower and meal Bassens seeds with hexane pellets Rapeseed meal 35% 2.35% Saipol From crushing process of rapeseed pellets seeds with hexane Rapeseed cold- 18% 11.7% Saipol From crushing process of rapeseed press cake seeds with no hexane (expeller) Soy protein 70% n.d. Efos concentrate Soy protein 90% n.d. Efos isolate ISP920H Brassica 40% 2.25% Saipol From crushing process of Brassica carinata meal Carinata seeds with hexane

[0192] Product Characterization

[0193] Dry Content

[0194] The material is placed in an aluminum cup with an amount of about 1.5 g. The exact weight is measured with an analytical balance with 4 digits after the decimal point. Then the cup is placed in a fan ventilated oven at 105° C. for 3 hours. Fan & valve aperture are set at 100% to accelerate water evaporation. Dry content is obtained by measuring the weight of the cup after being removed from the oven immediately or after conditioning in a desiccator to get sample at room temperature. Calculation of dry content is obtained by the calculation of material loss thanks to (1) and (2):

m.sub.loss=m.sub.0−m.sub.1  (1)

Where m.sub.0 and m.sub.1 are respectively the weight of the cup before being placed in the oven and after being placed in the oven.

[00001]$\begin{array}{cc}\mathrm{DC}\%=1-\frac{m_{\mathrm{loss}}}{m_{\mathrm{sample}}}& \left(2\right)\end{array}$

[0195] Where DC %, m.sub.loss and m.sub.sample are respectively the dry content, the weight of material loss and the weight of sample tested (m.sub.0−m.sub.cup).

[0196] An alternative method consists in using a moisture analyzer (Sartorius M50) to get the dry content or the moisture content. It enables to have the “atro” mode (i.e. moisture content in weight parts over dry composition) required for wood-based panel manufacturing. This method is also faster (i.e. few minutes versus 3 hours) but allows to test only one sample per round. The moisture analyser is preferably used for wood DC % determination prior to wood panel making.

[0197] Particle Size Determination

[0198] The particle size of ground samples is measured using a Malvern laser granulometer Mastersizer 3000. Sample material is injected through the dry injection tool of the analyzer. Refractive index and model used are respectively 1.52 and Mie to determine the particle size density profile. The main value of interest is the d50 previously described.

[0199] Viscosity Measurement

[0200] The viscosity of the dispersions and adhesive compositions was measured by using a rheometer (Haake MARS 40 by Thermo Scientific) equipped with a Pelletier heating/cooling system. The measurement device is a plate/plate system (20 mm diameter, 1 mm gap). Measurement is done with a dynamic mode (shear rate of 10 s.sup.−1, 50% shear and 20° C. temperature). The viscosity value was automatically determined after 5 minutes of measurement using Rheowin Job manager version 4.81.0000 (Haake Mess Tech, Germany).

[0201] Panels Characterization

[0202] Laboratory boards (200×200 mm) are cut to get samples for water resistance and internal bonding (IB).

[0203] Water resistance and IB are done respectively following standard ISO EN 317:1993 and ISO EN 319:1993 to get Thickness Swelling (TS) and IB. Apparatus used for all these measurements is the Imal (Italia), IBX700 model. The test results are mean values with their standard deviation.

[0204] Raw Material Microbiological Stability

[0205] In order to quantify microbiological stability, three tests were implemented to follow the evolution of the odor, surface appearance and biological activity of dispersions prepared from plant meals. At laboratory scale, approximately 300 g of dispersion were prepared in a polypropylene beaker of 400 mL and closed by a parafilm to avoid water evaporation. The three tests were monitored over time.

[0206] a) Odor

[0207] The perception of odor is subjective, and the following scale was used to rank odor level: [0208] 1: Standard odor of a fresh dispersion; [0209] 2: Slightly modified odor but not unpleasant; [0210] 3: Strongly modified odor but not unpleasant; [0211] 4: Slightly modified unpleasant odor; [0212] 5: Strongly modified unpleasant odor.

[0213] b) Visual Appearance

[0214] A scale for the appearance was implemented in order to have a qualitative evaluation of the visual evolution and is provided on FIG. 1.

[0215] For the “OK” sample, the dispersion of plant material is identical to T0 (fresh dispersion), in static state, with a liquid top layer having a light brown color.

[0216] For the “Fair” sample, the dispersion begins to contain solid aggregated (molds) on the top.

[0217] For the “Bad” sample, significant development of microorganisms (molds+bacteria) on the surface can be seen.

[0218] c) ATP-Metry

[0219] The last test to quantify the microbiological activity of the dispersion over time is ATP-metry.

[0220] ATP (adenosine triphosphate) is a molecule synthesized in all living cells (bacteria, yeasts, mammalian cells . . . ). When ATP breaks down in cells, it releases energy used by “cellular machines”, allowing them to work. It is their reserve of energy.

[0221] ATP can be quantified by a bioluminescence reaction, i.e. by light production caused by the chemical reaction between ATP and an enzymatic complex, luciferin-luciferase. This enzymatic complex, in presence of oxygen and magnesium, transforms the energy released by the hydrolysis of ATP into light. This light is measured by a luminometer, and the amount of light produced is proportional to the amount of ATP present in the measured sample, and thus living cells. Method, material and reagents used to realize this test were provided by GLBiocontrol (France).

[0222] The method follows these steps: approximately 30 g of dispersion were placed in a tube and centrifuged (model Sorvall ST8 from Thermo Scientific) at 3000 rpm for 10 minutes. This step was repeated twice with the supernatant for solid/liquid separation. A volume V of the final supernatant (no more than 2 mL) was placed in a sterile syringe including a sterile 0.45 μm porosity filter screwed at the output. The plunger of the syringe was then pushed to allow the sample to pass through the filter. Then 4 droplets of the reagent Dendridiag® IW (from GLBiocontrol, France) were sucked up by the syringe through the filter and then the contents of the syringe were pushed into a measuring tube provided for a luminometer. This tube was then tested into a luminometer Kikkoman PD30 to obtain the value R1 (in RLU: Relative Light Unit). Then, one droplet of the reagent named Standard 1000 (from GLBiocontrol) was added into the tube, and a new measurement with the luminometer is carried out to obtain the value R2 (in RLU). Finally, by using the equations described below, the bacteria equivalent concentration per milliliter was obtained.

[0223] With:

[00002]$\mathrm{Standard}=\frac{R2-R1}{1000}$$\left[ATP\right]=\frac{R1}{\mathrm{Standard}\times V}$ [0224] Standard=Value of the standard (RLU/pg ATP) [0225] R1=result on sample (RLU) [0226] R2=result on sample+standard (standard addition method) (RLU) [0227] V=filtered volume in milliliter [0228] [ATP]=ATP concentration (pg ATP/mL) [0229] 1 picogramme (pg) of ATP is about 1000 bacteria.

EXAMPLE 2

Preparation of Adhesive Compositions from Heat Ground Dry Material at Laboratory and Pilot Scales

Preparation of Heat Treated Ground Dry Material at Laboratory Scale

[0230] At the laboratory scale, raw material was ground using a laboratory grinder from Retsch model ZM 200. This equipment allows to get well define granulometry profile characterized by the d50 value (maximum size of 50% of the smallest particles in weight).

[0231] A ring sieve (80, 120 and 200 μm openings) is used to tailored particles size distribution and especially the d50 value in combination with mill speed (12000 and 18000 rpm). Higher is the sieve opening higher is the d50 and the lower is the speed, the higher is the d50.

[0232] Thermal treatment was applied on raw materials in an oven (UF75, Memmert, Germany) by controlling temperature and treatment time. To ensure the homogeneity of the treatment in the oven, raw materials were spread in thin layers (9±1 mm) on plates. Once the treatment is done, plates containing treated material were removed from the oven to let them cool down and equilibrate under room condition, and then was kept in a closed container for further analysis and use.

[0233] After the thermal treatment, the moisture content needs to be close to 0% (1% to 0%). If the value is higher, the thermal treatment was not done correctly and needs to be rerun. All products tested in the present Examples always had a moisture content lower than 1 wt %.

Preparation of Heat Treated Ground Dry Material at Pilot Scale

[0234] Two different processes were considered.

[0235] Grinding and Thermal Treatment:

[0236] Materials, in pellet shape, were first ground at the desired particle size (d50). Pilot plant is equipped with an impact mill grinder including a classifier from Hosokawa, model 200ZPS. After the classifier, the product is moved to Guedu dryer for thermal treatment. Guedu dryer is from De Dietrich Process System with a tank of 1600 L using a heating system with a double jacket and a powder impeller. The impeller ensures good product recirculation in the dryer and avoid particles agglomeration. The thermal treatment is realized by a temperature ramp and mixing speed.

[0237] Thermal Treat and Grinding:

[0238] In this variant, pellets are transferred to the Guedu dryer first for thermal treatment with the same protocol (heating ramp). This step allows to treat material before grinding and contributes to a first particle size reduction (pellet deagglomeration). Then the heat treated pellets are transferred to the mill (model 200ZPS, Hosokawa) for grinding operations to get the desired d50.

[0239] After the thermal treatment, the moisture content needs to be close to 0% (1% to 0%). If the value is higher, the thermal treatment was not done correctly and needs to be rerun. All products tested in the present Examples always had a moisture content lower than 1 wt %.

Preparation of a Heat Treated Dry Plant Meal Dispersion

[0240] From 20 wt % to 30 wt % of heat treated ground material (based on the targeted solid content accounting of the residual water adsorbed in the material and determined previously with the dry content test) were added in tap water at ambient temperature (20° C.) in a polypropylene beaker of 100 mL. The dispersion is mixed using a deflocculating blade (10 blades of 49 mm diameter, rod of 7 mm diameter) for two minutes.

Preparation of an Adhesive Composition

[0241] Adhesives containing different plant raw material in tap water, polyamidoamine epichlorohydrin (PAE) resin (commercially named Soyad CA 1920, from Solenis, 20 wt % dry content and a water content of 80 wt %) and crude glycerol (vegetable glycerin 80 from Saipol, containing at least 80 wt % of glycerol) were formulated.

[0242] A pre-mix of all liquid products was first made with tap water, glycerol, and PAE resin. A mix of 47.37 wt % of glycerol in water was first blended at ambient temperature in a polypropylene beaker by using a deflocculating blade (10 blades of 49 mm diameter, rod of 7 mm diameter) for two minutes at 1000 rpm until solution becomes homogeneous. Then PAE resin was added at a weight ratio glycerol:PAE 1:0.108 based on dry content. The mixture is blended until solution becomes homogeneous once again (no phase separation).

[0243] Then, thermally treated or untreated ground plant material was blended for 5 minutes at 1000 rpm with the pre-mix at a weight ratio glycerol:plant material of 1.5:1, based on dry content (residual water in the ground plant meal need to be took into account in the recipe) until an homogeneous dispersion is obtained.

[0244] Finally, the pH of the adhesive formulation is adjusted at 8.1 (±0.1) by addition of a solution of NaOH at 5 mol/L.

Preparation of Particle Boards at Laboratory Scale

[0245] To manufacture laboratory particle boards, the adhesive composition is blended with wood particles using a planetary blender (pluton, mineapolis) with a paste impeller. An amount of 600 g of wood is introduced in the blender tank after moisture content determination which is expected to be around 4.5% atro.

[0246] The adhesive composition is then weighed and introduced with a syringe to the wood furnish while the blender is running with the lowest speed. A 5 minutes mixing time is applied to ensure homogenous distribution of the glue with the wood furnish.

[0247] When a target moisture for wood furnish before pressing is required, water could be added to the wood before the adhesive. The adequate value is calculated by considering the targeted value to reach and removing from this calculation the water already adsorbed in the wood and the water contained in the adhesive composition. Standard targeted Mat (resin impregnated wood before hot pressing) moisture content value is about 10-12% atro. The real value will be checked after blending with the moisture analyzer equipment. At the end of this step, an impregnated wood sample ready to form a laboratory size particle board is obtained.

[0248] A 200×200×200 mm wood forming box is filled with impregnated wood (Wood+Adhesive+water) sample weighed to achieve a particle board with a density of 650 kg/m.sup.3 at a thickness of 12 mm (final thickness is obtained thanks to a stainless-steel mold of 12 mm thick). After that, impregnated wood is cold pressed by hand to form a mat. The mat is hot pressed to a thickness of 12 mm for 5 minutes at a press platen temperature of 180° C. After pressing, thickness and weight of the particle board samples were measured and recorded for control. Then the particle board was placed in a conditioning room at 20° C. and 65% r.h. (relative humidity) for at least one day. For each adhesive composition, 2 boards were made.

EXAMPLE 3

Determination of a Lower Temperature Range

[0249] In a first step, it was evaluated if there is a minimum temperature to apply a thermal treatment and quantify any thermal barrier to overpass to get the treatment happening. The efficiency of the treatment is based on viscosity reduction versus a reference material not treated. Temperatures from room temperature to 105° C. were tested. An overnight time for the treatment was chosen to ensure enough time to get something quantifiable. Viscosity was checked at solid content from 25 to 30 wt % to quantify benefits even if the current usage is closer to 20 wt % for value discrimination purpose. Dispersions having different solid contents prepared according to Example 2 (laboratory scale) from ground rapeseed meal having a d50 at 30 μm were tested. The results are shown on FIG. 2.

[0250] The results show that a treatment done at 50° C. and 70° C. has an insignificant influence on viscosity of these dispersions. However, the thermal treatment at 105° C. overnight dramatically reduces the viscosity of ground meal dispersions whatever is the solid content (% dispersion). The biggest drops obtained thanks to thermal treatment were observed at high solid content. 105° C. appears to be closed to the lower temperature limit to get an efficient thermal treatment.

EXAMPLE 4

Thermal Treatment Optimization

[0251] To optimize the thermal treatment, a small quantity of the same ground rapeseed meal was conditioned in an oven only 2 h versus overnight, and dispersions were prepared with a solid content of 25 wt % (process according to Example 2, laboratory scale). The viscosity of the dispersions was measured and is indicated in Table 2.

TABLE-US-00002 TABLE 2 viscosity of dispersions prepared from ground rapeseed meal Viscosity Temperature Time (25% dispersion) No treatment 1252 mPa .Math. s 105° C.  2 h 1252 mPa .Math. s 105° C. 12 h 200 mPa .Math. s

[0252] At 105° C., 2 h was not enough to get a positive impact especially versus a 12 h time as in Example 3. It highlights the need to move to higher temperature to shorten treatment time. The tests at higher temperatures were handle on rapeseed meal and pellets: heat treatment was done on the ground meal (after grinding) and on the meal pellets (before grinding). The viscosity of the dispersions (25 wt % solid content) prepared from rapeseed meal and rapeseed meal pellets are indicated in Tables 3 and 4 respectively.

TABLE-US-00003 TABLE 3 viscosity of dispersions prepared from rapeseed meal Rapeseed meal Viscosity, 25% Relative Process Process dispersion viscosity, temperature time (min) (mPa .Math. s) Uncertainty %  20° C. 0 495 74.25 100.0% 120° C. 15 387 58.05 78.2% 30 322 48.3 65.1% 45 280 42 56.6% 150° C. 15 161 24.15 32.5% 30 80 12 16.2% 45 64 9.6 12.9% 200° C. 5 67 10.05 13.5%

[0253] The first value (20° C., 0 min) corresponds to the untreated sample. One can observe a different value than in Table 2 even if it is the same raw material origin obtained at a different period of time (495 mPa.Math.s vs. 1252 mPa.Math.s). This difference is not surprising as Rapeseed is a natural product, its composition and characteristics are changing based on, for example, season, origin, process parameter, and induce viscosity variations.

[0254] At 120° C. for a process time of 30 and 45 minutes, viscosity values are in between 322 to 280 mPa.Math.s, evidencing a clear trend of viscosity reduction versus time to 57% of initial viscosity value.

[0255] At 150° C., viscosity values are even lower and in between 161 and 61 mPa.Math.s. In other words, a treatment at 150° C. for 15 min is more efficient than 120° C. for 45 min. At 150° C. the viscosity drop from 160 to 80 mPa.Math.s by increasing treatment time from 15 to 30 min which correspond to 32% to 16% of the initial value. When the treatment time is increased to 45 min, viscosity decreases to 67 mPas i.e. 13% of the initial value. 150° C. and 30 min appears to be a good compromise between time and viscosity decrease at this stage.

[0256] At 200° C., only one treatment time was tested (5 min), giving a value of 67 mPa.Math.s (13.5% of the initial value) which is equal to 150° C. and 45 min treatment. It is an even more efficient condition. However, at the laboratory scale it will be hard to control a so short treatment time. This condition is more suitable for a continues process rather than a batch process.

[0257] Same approach was conducted on Rapeseed meal pellets:

TABLE-US-00004 TABLE 4 viscosity of dispersions prepared from rapeseed meal pellets Rapeseed meal pellets Viscosity, 25% Relative Process Process dispersion viscosity, temperature time (min) (mPa .Math. s) Uncertainty %  20° C. 0 470 70.5 100.0% 120° C. 15 272 40.8 57.9% 30 222 33.3 47.2% 45 204 30.6 43.4% 150° C. 15 99 14.85 21.1% 30 58 8.7 12.3% 45 45 6.75 9.6%

[0258] The reference product (20° C., 0 min) has a viscosity of 470 mPa.Math.s, which is close to the previous value which correspond to the experimental error using the same material. At 120° C., viscosity values are in between 272 and 200 mPa.Math.s (58 to 43% of the initial value). It appears that viscosity reduction obtained on meal pellets is more significant than on ground meal.

[0259] At 150° C., viscosity reduction is close to 10% (for 30 and 45 min) which is close to what the values obtained with ground meal. It seems that the advantage of pellet shape versus ground meal depends on temperature.

[0260] No measurement was done at 200° C. as it becomes too high. Pellets start to burn. In conclusion, on powder meal, preferred temperature range will be 150 to 200° C. to get a significant viscosity reduction. Higher is the temperature, lower is the time required to get the lowest viscosity possible. On meal pellets, even if heat treatment is better for intermediate temperature and intermediate performance, the preferred temperature range will also be 150 to 200° C.

EXAMPLE 5

Thermal Treatment Robustness: 150° C. During 30 Min for Various Plant Meals

[0261] A clear benefit of thermal treatment has been observed with rapeseed meal with an optimum temperature in between 150 to 200° C. and less than 30 min. The same set of experiments was carried out with another plant meal which is sunflower meal, dispersions being prepared with a solid content of 25 wt % (process according to Example 2, laboratory scale). Treatments have been done only on ground sunflower meal, the viscosity of the dispersions being indicated in Table 5.

TABLE-US-00005 TABLE 5 viscosity of dispersions prepared from sunflower meal Sunflower meal Viscosity, 25% Relative Process Process dispersion viscosity, temperature time (min) (mPa .Math. s) Uncertainty %  20° C. 0 64000 17920 100.0% 150° C. 15 44500 12460 69.5% 30 14800 4144 23.1% 45 1796 502.88 2.8% 175° C. 15 211 59.08 0.3% 30 70 19.6 0.1% 200° C. 5 190 53.2 0.3% 15 46 12.88 0.1%

[0262] The reference value is much higher for sunflower meal than for rapeseed meal for the same dry content, 64000 mPa.Math.s versus 1200-500 mPa.Math.s respectively.

[0263] At 150° C., a significant viscosity reduction to 23% and 3% of the initial value was observed for 30 and 45 min treatment time respectively. There is a clear link between treatment time and viscosity reduction.

[0264] At 175° C., the effect is even more pronounced and it is possible to get viscosity values equivalent to heat treated rapeseed even if the reference viscosity of the sunflower meal dispersion is much higher. At 200° C., equivalent viscosity values could be achieved in a shorter time.

[0265] In conclusion, Sunflower meal needs a higher temperature to get viscosity values similar to rapeseed. However, with the same thermal treatment (same time and temperature), same level of viscosity reduction could be obtained. At 150° C. for 30 min, rapeseed exhibits a viscosity reduction of 12% while sunflower exhibits a viscosity reduction of 23%.

[0266] Even if thermal treatment needs to be adapted based on raw material origin, a temperature of 150° C. and time of 30 min was set for comparison purpose. At this setting any possible improvement brought by thermal treatment could be observed.

[0267] To check quickly the efficiency of thermal treatment, a quick test could be moisture measurement. In general, rapeseed meal pellet contains about 11 wt % moisture.

[0268] When pellets are ground, the moisture content decreases based on the micronization process. This moisture content could range from 10 wt % to 6 wt % for an impact mill micronizer. This range is usually linked to the final particle size reduction: the dryer, the smaller. After the thermal treatment, the moisture content needs to be close to 0% (1% to 0%). If the value is higher, the thermal treatment was not done correctly and needs to be rerun. All products tested in the present Examples always had a moisture content lower than 1 wt %.

[0269] Dispersions with all samples (with and without thermal treatment) were made at several solid contents to account of their different behavior in term of processability while used (as observed in between Sunflower and Rapeseed). Results are summarized in the following Table 6, wherein the reduction of viscosity between untreated and heat treated material is indicated in parenthesis.

TABLE-US-00006 TABLE 6 Viscosity values (mPa .Math. s) of raw materials in water dispersion for several solid contents with viscosity decrease percentage Solid content (wt %) 5% 10% 15% 20% 25% 30% 35% Wheat draff No treatment 58 275 2520 150° C./30 min 48 210 800 (−17%) (−24%) (−68%) Corn draff No treatment 60 200 930 5100 150° C./30 min 60 48 230 (−70%) (−95%) (−95%) Flaxseed No treatment 190 2920 meal 150° C./30 min 20 565 (−89%) (−81%) Soy meal No treatment 160 370 2200 150° C./30 min 50 40 110 (−69%) (−89%) (−95%) Rapeseed No treatment 410 1600 cold-press 150° C./30 min 40 900 cake (−90%) (−44%) (expeller) Soy protein No treatment 33 670 270000 concentrate 150° C./30 min 14 62 580 (−58%) (−91%) (−99%) Soy protein No treatment 40 15100 isolate 150° C./30 min 17 50 (−57%) (−99%) Brassica No treatment 35 260 65000 carinata 150° C./30 min 35 40 850 meal (0%) (−84%) (−99%)

[0270] One can observe different behaviors from one product to another. All products (containing at least 15 wt % of proteins) exhibit a benefit of thermal treatment which leads to a dramatic reduction of viscosity. It appears that this reduction of viscosity is even more impressive for high protein content materials like soy protein concentrate and isolate. Aside of the impact of thermal treatment, it appears that material origin has an impact on viscosity while dispersed in water and, for this reason, solid content range has been adapted each time. High protein content material like soy protein isolate, soy protein concentrate, and soy meal can be processed only at a maximum of, respectively, 5%, 15% and 15% solid contents in weight percentages. When a thermal treatment is applied, this solid content could be increased up to respectively 10%, 20% and 20%. Other meals like rapeseed cold press cake and Brassica carinata meal can be processed at a higher solid content without thermal treatment up to respectively 15% and 20% and with thermal treatment up to respectively 20% and 20%.

[0271] Linseed meal exhibits a different behavior with a very low solid content to be processable (5 wt %).

[0272] In conclusion, the benefits of thermal treatment are not equal from one material to the another. It correlates partially to protein content in this investigated range.

EXAMPLE 6

Thermal Treatment Robustness: 150° C. During 30 Min for Rapeseed Meal

[0273] In order to confirm thermal treatment advantages, various rapeseed meal origins (lot number: GCXX-12/18 and LMXX-26/18) were tested with the same protocol as described in Example 2 (150° C. and 30 min, laboratory scale) to check if these parameters duly always decrease viscosity or need to be adjusted on a material origin. The protocol (150° C. and 30 min) has been re-applied on various grinded meal (various origin & granulometry) at 2 solid contents (23 wt % & 25 wt %). Only the results at 23 wt % solid content are presented on FIG. 3 since same trends were found for both solid contents.

[0274] One can observe that meal origin affect viscosity (it has been confirmed with other meal origin). Granulometry d50 affect dramatically viscosity and processability consequently. When a thermal treatment is applied, it becomes harder to differentiate, based on viscosity values, meal origins or the impact of granulometry. It means that, thermal treatment, aside of bringing a general processability improvement thanks to viscosity reduction, could “erase” the impact of granulometry and meal origin.

[0275] To extend these statements to other conditions, dispersions were prepared at different solid contents from rapeseed meals of different origins (GCXX-12/18 and LMXX-26/18) having a d50 at 30 μm with and without thermal treatments. The viscosity of the dispersions was measured and is presented on FIG. 4. Viscosity reduction was observed with solid content from 20 wt % to 27 wt % enabling to extent solid content range of usage up to 30 wt % (it was not possible to achieve a low enough viscosity to prepare dispersions at 30 wt % solid content from non-treated rapeseed meal).

[0276] Finally, all these laboratory results confirm interest of thermally treated ground rapeseed meal. The main benefit is a decrease of viscosity, which allows an improvement in the ease of use of adhesive. It also reduces meal origin impact on viscosity and thus the reduction of lot-to-lot variation.

EXAMPLE 7

Evaluation of Microbiological Stability

[0277] To check the impact of thermal treatment, odor and surface aspect evolutions were monitored at a laboratory scale. It enables to assess the impact of thermal treatment on product stability. As all-natural products when dispersed in water, bacteria and fungi will start to develop and induce odor and a modification of the aspect of the dispersion. These evolutions are not desirable for customers and could impact performances. It was determined that, without any thermal treatment, odor starts to develop after 3 days. Consequently, any stop of the production system for more than 2 days requires a complete system flush and cleaning.

[0278] Evaluations presented in this Example were conducted with a 20 wt % solid rapeseed micronized meal dispersion in water (prepared according to Example 2: “Grinding and thermal treatment” at pilot scale) without stirring (at rest).

[0279] In order to quantify microbiological stability, the three tests described in Example 1 (“Raw material microbiological stability”) were implemented to follow the evolution of the odor, surface appearance and biological activity of the dispersion.

[0280] The results regarding the odor and aspect of the dispersions are presented in Table 7 and FIG. 5 respectively.

TABLE-US-00007 TABLE 7 Evaluation of the odor of dispersions of rapeseed meal J0 J1 J2 J3 J4 J5 J6 J7 J8 J9 J10 Rapeseed meal 1 4 5 5 5 5 without treatment Rapeseed meal 1 3 3 3 4 5 with temperature ramp up to 115° C. in pilot dryer

[0281] As observed in Table 7, the thermal treatment enables to delay odor appearance from 3 to 7 days. Moreover, surface aspect from pictures presented on FIG. 5 is better with a dispersion using thermally treated rapeseed meal. No development of fungi or mould is observed after 7 days whereas it is noticeable after only 3 days with rapeseed meal without treatment. These two observations evidence a significant improvement of odor and aspect versus time in addition to an ease of use, for the present invention.

[0282] In order to confirm these results, an industrial scale batch (300 L) has been done with thermally treated rapeseed meal at 20 wt % solid in water. To control the microbiological development, the ATP-metry method has been used and the results are shown on FIG. 6.

[0283] Development of the strong odor of dispersion using thermally treated meal starts sooner at industrial scale (5 days) than at laboratory scale (7 days). There is a strong correlation between microorganism concentration curve and odor appearance.

EXAMPLE 8

Pilot Scale: Thermal Treatment of Pellets and then Grinding

[0284] This Example was conducted according to the procedure described in Example 2 (pilot scale).

[0285] Temperature of 115° C. was applied on a sample of 450 kg.

[0286] Thermal treatment at pilot scale was handled by loading materiel in the dryer. Then, a temperature ramp was applied to achieve the targeted temperature. When the targeted temperature was achieved, heating is stopped to let the material cool down below 80° C. to be able to condition it safely in bags. Then the material could be ground directly (still warm) or cooled to room temperature overnight. All treatments were done under atmospheric pressure and are summarized in Table 8.

TABLE-US-00008 TABLE 8 Treatment conditions of rapeseed meal pellets Viscosity of a 25 wt % ground Thermal treatment Flow rapeseed Raw Treated Temperature Grinding Particle rate meal material Temperature mass profil conditions size kg/h dispersion Rapeseed / / / cold pellets 30 μm 80 1177 mPa .Math. s meal pellets 115° C. 450 kg heating 101 min hot pellets 30 μm 56  237 mPa .Math. s GC 12/18-06 cooling 105 min cold pellets 30 μm 92.4

[0287] When no thermal treatment is applied, mill throughput is about 80 kg/h. During the first heat test, the material was ground directly after the thermal treatment (115° C.) while pellets were still warm (about 80° C.). One can observe that the throughput is dramatically reduced to 56 kg/h. Once pellets are cooled down to room temperature (overnight) the throughput increases up to 92 kg/h.

[0288] The viscosity of dispersions prepared at 25 wt % solid content from rapeseed meal pellets treated as described above (and after cooling) was measured and is presented on Table 8. From this Table 8, decrease of viscosity can be observed when a thermal treatment is applied. It clearly demonstrates the efficiency of applying a thermal treatment on the viscosity reduction. The feasibility tests at the laboratory scale and at the pilot scale show that this treatment is able to decrease the viscosity.

[0289] Viscosity of the dispersion of ground rapeseed meal pellets has been measured at several solid contents versus the untreated material and the results are shown on FIG. 7. Once again, thermal treatment significantly decreases viscosity of ground rapeseed meal in dispersion with water for all solid contents from 23 to 30 wt %. An acceptable viscosity from the process point of view could be get to solid content up to 27 wt % versus untreated material where the maximum acceptable solid content is 23 wt %.

EXAMPLE 9

Pilot Scale: Grinding and then Thermal Treatment of Pellets

[0290] This Example was conducted according to the procedure described in Example 2 (pilot scale).

[0291] In this approach, pellets were first ground at an industrial scale, and then thermally treated into the same pilot dryer used previously. Tested parameters are the same as in Example 8. The main goal is to determine efficiency of this second approach and assess the impact of thermal treatment order. From the process point of view, this method was easier to handle (no cooling required) and gave the highest throughput.

[0292] Viscosity curves of a dispersion of ground rapeseed meal (d(50)=30 μm) without treatment and with a thermal treatment at 115° C. were made, the solid content varying between 20 wt % and 30 wt %. The results are shown on FIG. 8.

[0293] Again, thermal treatment significantly decreases viscosity of ground rapeseed meal in dispersion with water at a comparable level than previously observed at laboratory scale from this experiment. However, it can be noted that this order is more effective than thermal treatment before grinding (see Example 8, FIG. 7).

EXAMPLE 10

Viscosity of Ground Dry Plant Material in Aqueous Dispersion Depending on pH of the Dispersion

Preparation of Dispersions

[0294] 80 g dispersions were prepared by adding from 20 wt % to 30 wt % of untreated or thermally treated (150° C. for 30 minutes according to Example 2 at laboratory scale) ground plant material (based on the targeted solid content accounting of the residual water adsorbed in the material and determined previously with the dry content test described in Example 1) in tap water at ambient temperature in a polypropylene beaker of 100 mL. Each dispersion is mixed using a deflocculating blade (10 blades of 49 mm diameter, rod of 7 mm diameter) for two minutes, and until an homogeneous dispersion is obtained. The particle size of the used ground materials is about d(50)=30 μm. Then, the pH of the dispersion is adjusted by addition of a solution of NaOH at 5 mol/L to increase pH, or by addition of a solution of HCl at 5 mol/L to decrease pH. [0295] Results

[0296] Viscosity of dispersions made with sunflower meal (20 wt % dispersion in water) and rapeseed meal (30 wt % dispersion in water) was measured using the rheometer (within 15 minutes maximum) as described in Example 1, and is presented on FIG. 9 for sunflower meal and on FIG. 10 for rapeseed meal.

[0297] Viscosity of dispersions made with thermally treated ground sunflower or rapeseed meal is lower than viscosity of dispersions made with the corresponding untreated meals. Thus, the thermal treatment process contributes to improve processability of these ground plant-based dispersions by decreasing viscosity, whatever the pH of these dispersions.

EXAMPLE 11

Viscosity of Adhesive Compositions

[0298] To check if the benefit of viscosity reduction is kept for an adhesive composition, adhesive compositions were prepared as described in Example 2 (“Preparation of an adhesive composition”), with untreated or heat treated ground plant materials having different origins. When a heat treatment was applied, it was conducted as described in Example 2 (laboratory scale, 150° C., 30 min).

[0299] Viscosity of these adhesive compositions was measured using the rheometer, and is presented in Table 9:

TABLE-US-00009 TABLE 9 Viscosity values (mPa .Math. s) of adhesive compositions comprising different ground plant materials Ground plant material used in adhesive Untreated plant Thermally treated plant composition material material Sunflower meal 11000 mPa .Math. s 360 mPa .Math. s Canola meal 190 mPa .Math. s 150 mPa .Math. s Rapeseed meal 280 mPa .Math. s 230 mPa .Math. s Wheat draff 980 mPa .Math. s 270 mPa .Math. s

[0300] One can observe different behavior from one product to another. Sunflower meal exhibits a huge benefit of thermal treatment, which lead to a dramatic reduction of viscosity. The same trend was observed for adhesives using wheat draff. Thermal treatment of canola meal and rapeseed meal make also possible to decrease adhesive viscosity. However, viscosity of these adhesives with untreated meal was already low, therefore the treatment only slightly decreases the viscosity. Thermal treatment is effective for these raw materials, and in some cases, a very significant reduction in viscosity is observed.

EXAMPLE 12

End Use Performance Evaluation

[0301] The adhesive compositions prepared in Example 10 are used in this Example 11 to make wood particle boards. The wood particle boards were prepared as described in Example 2 (“Preparation of particle boards at laboratory scale”). Based on 100 dry parts of wood particles, the added adhesive equivalent represents 6 parts of glycerol, 4 parts of ground plant-based material and 0.65 part of dry content PAE resin. The moisture content of the mat is around 11% atro.

[0302] Then, internal bonding and thickness swelling were measured as described in Example 1, and are presented on FIGS. 11 and 12 respectively.

[0303] A no significant variation of the internal bonding due to thermal treatment is observed for all adhesives. Moreover, adhesives made with sunflower meal show the best performances.

[0304] For water resistance, untreated and thermally treated plant-based materials gave similar level of performance accounting standard deviation. However, an exception can be noted concerning adhesives made with canola meal, a slight decrease of the water resistance is observed. Sunflower meal gave the best water resistance performance, whereas the lowest water resistance is observed for adhesives based on wheat draff.

[0305] Finally, the processability of the adhesive can be improved for all of the studied ground plant-based material by applying a thermal treatment to them. This treatment has the ability to decrease adhesive viscosity, especially for adhesives based on ground sunflower meal, with no impact on mechanical performances and water resistance of wood particle boards.

EXAMPLE 13

Properties of Dispersions and Adhesive Compositions Obtained from Heat Treated Dry Plant Meal According to the Invention and from Plant Meal Heat Treated in Aqueous Conditions

[0306] Thermal treatment of plant-based raw materials

[0307] Soy flour (7B soy flour grade supplied by ADM, obtained by grinding soy meal) and ground sunflower meal (sunflower meal pellets ground at a granulometry of d.sub.50=30 μm) were heat-denatured in water and then mixed with urea (commercial grade supplied by YARA France) to produce a soy/urea aqueous product (Formula 1A in Table 10 below) and a sunflower/urea aqueous product (Formula 1B in Table 11 below), following this procedure: water was charged into a closed laboratory reactor IKA LR 1000 control equipped with a heating device, temperature controller and mechanical stirrer. The plant-based raw material was added to the water at room temperature over a period of three minutes. The mixture was stirred for five minutes to homogeneity and then heated to 90° C. over thirty minutes. The reaction was held at 90° C.±2° C. for one hour with stirring at 80 rpm. Then, the urea was added to the plant-based raw material and the mixture was held at 90° C.±2° C. with stirring for one hour. Then, heating was stopped to let cool the mixture and store it for use in plastic bottles at room temperature. A measurement of the solid content of these products was performed.

TABLE-US-00010 TABLE 10 Formula 1A Sequence Ingredient Total mass (g) Solid content (g) 01 Water 660.3 0 02 Soy Flour 150 143 03 Urea 143 143 Total 953.3 286 % Solid content 30

TABLE-US-00011 TABLE 11 Formula 1B Sequence Ingredient Total mass (g) Solid content (g) 01 Water 660.3 0 02 Sunflower meal 150 143 03 Urea 143 143 Total 953.3 286 % Solid content 30

[0308] In order to compare this thermal treatment in aqueous dispersion (wet thermal treatment) and thermal treatment according to the present invention (dry thermal treatment), aqueous dispersions containing thermally treated soy flour (150° C./30 min in dry condition) (Formula 2A) and thermally treated sunflower meal (150° C./30 min in dry condition) (Formula 2B) according to the present invention (dry thermal treatment at laboratory scale, Example 2, second paragraph of “Preparation of heat treated ground dry material at laboratory scale”) mixed with urea were prepared to reach the same plant meal/urea ratio and the same solid content of these dispersions as respectively Formulas 1A and 1B. For all products (Formulas 1A, 1B, 2A and 2B), dry content and viscosity were measured.

[0309] In a second step, this protocol was repeated but without addition of urea. In this way, 4 aqueous dispersions with a targeted dry content of 15 wt % was prepared containing a thermally treated soy flour in dispersion (90° C./1 h in aqueous dispersion) (Formula 3A) and a thermally treated sunflower meal in dispersion (90° C./1 h in aqueous dispersion) (Formula 3B), a thermally treated soy flour (150° C./30 min in dry condition) in dispersion (Formula 4A) and a thermally treated sunflower meal (150° C./30 min in dry condition) in dispersion (Formula 4B) according to the present invention. A measurement of the dry content and viscosity of these products was realized.

Preparation of Adhesive Compositions

[0310] The pH of Formulas 1A and 2A were adjusted to reach the value of 7 with stirring by using a H.sub.2SO.sub.4 solution (1 mol/L) or a NaOH solution (1 mol/L) depending of the starting pH. These two adhesive compositions are named respectively Formula 5A and Formula 5B. Viscosity of these two Formulas was measured.

[0311] 5% (dry weight/dry weight) of PAE was added to Formula 5A (based on Soy flour+urea contents), and 5% (dry weight/dry weight) of PAE was added to Formula 5B (based on soy flour+urea contents), at room temperature with agitation in a 100 mL beaker using a mixing blade and an overhead mechanical stirrer. These two adhesive compositions are named respectively Formula 6A and Formula 6B. Viscosity of these two Formulas was measured.

[0312] Protocol of Adhesion Performances Characterization

[0313] Adhesion performances of Formulas 5A, 5B, 6A and 6B were characterized following this protocol: The Automated Bonding Evaluation System (ABES) from AES, Inc. was used to measure the shear strength of the adhesive bond of the different samples as developed over time under specific pressing times/temperatures. Two ply were cut using the ABES stamping apparatus from Eastern White Pine veneer such that the final dimensions were 11.7 cm along the grain, 2.0 cm perpendicular to the grain and 0.08 cm thick. The adhesive to be tested was applied to one end of the sample such that the entire overlap area is covered, being in the range of 4-5 mg/cm.sup.2 on a wet basis. The sample was then bonded to a second veneer (open time of less than 15 seconds to ensure excellent transfer) and placed in the ABES unit such that the overlap area of the bonded samples was 0.5 cm by 2.0 cm. All samples were pressed for 9 different times (10, 30, 60, 90, 150, 210, 270, 360 and 500 seconds) at 120° C., followed by a cooling step of 4 seconds thanks to pressurized air, and finally tested within the ABES unit itself within seconds after cooling.

[0314] Results and Discussions

[0315] The results of the product characterization from Formulas 1A, 1B, 2A and 2B are shown in Table 12:

TABLE-US-00012 TABLE 12 Dry content and viscosity of Formulas 1A, 1B, 2A and 2B Viscosity Formula Dry content (%) (mPa .Math. s) 1A 28.3 4720 1B 29.2 11300 2A 28.3 630 2B 29.2 70

[0316] One can notice that viscosity of Formulas 2A and 2B, using dry thermally treated raw materials according to the present invention is much lower than viscosity of products made with a thermal treatment in aqueous dispersion (Formulas 1A and 1B). Thus, the present invention enables a decreased viscosity with an equivalent dry content.

[0317] The preparation procedure was repeated without addition of urea, (Formulas 3A, 3B, 4A and 4B) and results are presented in Table 13:

TABLE-US-00013 TABLE 13 Dry content and viscosity of Formulas 3A, 3B, 4A and 4B Viscosity Examples Dry content (%) (mPa .Math. s) 3A 14.83 2257 3B 14.47 3685 4A 14.83 55 4B 14.47 50

[0318] The same trend was observed. The dry thermal treatment according to the present invention enables a much lower viscosity with a similar dry content of the aqueous dispersion.

[0319] Then, Formulas 5A, 5B, 6A and 6B were prepared and characterized. Values of viscosity for all Formulas are shown in Table 14:

TABLE-US-00014 TABLE 14 Viscosity of Formulas 5A, 5B, 6A and 6B Viscosity Formula (mPa .Math. s) 5A 3694 5B 2215 6A 8667 6B 537

[0320] Once again, adhesive compositions formulated with thermally treated soy flour (in dry condition) according to the present invention showed a lower viscosity than thermally treated soy flour (in wet condition), (40% lower viscosity for Formula 5B compared to Formula 5A, i.e. without PAE addition), and with a better improvement in the case of PAE addition (93% lower viscosity for Formula 6B compared to Formula 6A, i.e. with 5 wt % PAE addition).

[0321] Finally, the adhesion performance of these different products was characterized following the described protocol using the Automated Bonding Evaluation System (ABES). The results are plotted in FIG. 13 relative to press time to determine the relative strength development of these different adhesives as a function of time.

[0322] Formula 5B demonstrates the better adhesion properties of an adhesive obtained using a dry thermally treated soy flour according to the present invention, without PAE addition, in comparison with an adhesive obtained using a soy flour thermally treated in aqueous conditions (Formula 5A). With PAE addition, Formulas 6A and 6B showed similar adhesion performances over time for both thermal treatments. But the thermal treatment according to the present invention enabled a much lower viscosity, as seen previously.

EXAMPLE 14

Properties of Adhesive Compositions Obtained from Heat Treated Dry Plant Meal According to the Invention and from Acid Denatured Plant Meal

[0323] Acid Denatured Adhesive preparation

[0324] According to acid treatment of US 2011/0048280 A1 patent application (Example 7 of US 2011/0048280 A1), soy flour (ground soy meal) was acid-denatured and then combined with urea to produce a stable soy/urea aqueous product (Formula 1). The formula used for this experiment is provided in Table 15:

TABLE-US-00015 TABLE 15 Formula 1 Sequence Ingredient Wet mass (g) Solids (g) 01 Water 304.3 0 02 Sodium Bisulfite 1.56 1.56 03 Soy Flour 164.5 156.3 04 Urea 156.3 156.3

[0325] Water was loaded in a 1 L beaker equipped with an overhead mechanical stirrer. The sodium bisulfite was added to the room temperature water followed by addition of the soy flour over a period of five minutes. The mixture was stirred for 30 minutes at room temperature. Sulfuric acid was then added dropwise to the rapidly stirring mixture until a pH of 3.5 was reached and, subsequently, held for an additional 30 minutes. Then, sodium hydroxide was added slowly to the rapidly stirring mixture to raise the pH to 7, and the mixture was stirred for 5 minutes. Urea was then quickly added to the rapidly stirring acid denatured soy mixture and allowed to stir for an additional 5 minutes. The adhesive was finally stored for use in plastic bottles while being maintained at room temperature. The adhesive (Formula 1) was a very homogeneous light tan, creamy product. The dry content of the final adhesive was measured as 43.77 wt %. A measurement of the viscosity was carried out.

[0326] In order to compare this acid-denatured treatment and dry thermal treatment according to the present invention, an aqueous dispersion containing thermally treated soy flour (150° C./30 min in dry condition) (Formula 2) with urea was prepared to reach the same soy/urea ratio (1:1) and the same dry content (43.77 wt %) as the adhesive prepared above (formula of Table 15). A measurement of the viscosity was carried out.

[0327] Adhesives Combined with PAE

[0328] 20% (w/w) of PAE was added to Formula 1 on a dry basis, and 20% (w/w) of PAE was added to Formula 2 on a dry basis, at room temperature with agitation in a 100 mL beaker using a mixing blade and an overhead mechanical stirrer. These two adhesives are named respectively Formula 3 and Formula 4, and have a pH of about 7. Viscosity of these two Formulas was measured.

[0329] Protocol of Adhesion Performance Characterization

[0330] Adhesion performances of Formulas 1, 2, 3 and 4 were characterized following the protocol described previously (Example 13 above) using The Automated Bonding Evaluation System (ABES). All samples were pressed for 4 different times (10, 30, 60 and 90 seconds) at 120° C. and tested within the ABES unit itself within seconds after pressing.

[0331] Results and Discussions

[0332] Viscosity of Formulas 1, 2, 3 and 4 is shown in Table 16:

TABLE-US-00016 TABLE 16 Viscosity of Formulas 1, 2, 3 and 4 Viscosity Formula (mPa .Math. s) 1  5294 2 355000* 3  992 4 29320 *This high viscosity value results from the high dry content of the formula (43.77 wt %) and the presence of urea (dry content: 21.88 wt %) in the formula

[0333] The acid-denatured soy flour/urea adhesive of Formula 1 exhibits a lower viscosity than the dry thermally treated soy flour/urea adhesive of Formula 2. This behavior can be explain by plant-based material modification due to acidification. Indeed, a very acidic environment enables separation of amino acids groups from protein chains. Protein chains become shorter and physical interactions become weaker. This can therefore induce an important decrease of viscosity. The same trend was observed after addition of PAE. Viscosity of Formula 3 (with acid-denatured soy flour) is lower than viscosity of Formula 4 (with dry thermally treated soy flour).

[0334] The adhesion performance of these different products was characterized following the described protocol using the Automated Bonding Evaluation System (ABES). The results are plotted in FIG. 14 relative to press time to determine the relative strength development of these different adhesives as a function of time.

[0335] Formulas 1 and 2 showed similar adhesion performances, but these performances are too low to obtain a good adhesive without PAE addition. On the contrary, Formula 4 demonstrates the better adhesion properties of an adhesive using a dry thermally treated soy flour according to the present invention with PAE addition, in comparison with an adhesive using an acid-denatured soy flour with PAE addition (Formula 3) according to US 2011/0048280 A1 patent application. Therefore, even if adhesives prepared with acid-denatured soy flour have a lower viscosity, adhesion performances are very low to obtain a good adhesive for wood-based panels. The acid-denatured treatment decreases adhesion performances of plant-based raw material because of separation of amino acids groups from protein chains. On the contrary, dry thermal treatment according to the present invention enables to obtain sufficient adhesive performances to use dry thermally treated plant-based material associated with PAE as a wood-based panel adhesive.

EXAMPLE 15

Viscosity of Dispersions Prepared from Heat Treated Wound Plant Meal and Wound Plant Meal Pressed Hot

[0336] Materials and Methods

[0337] An expeller rapeseed meal from Sanders Bretagne (St-Gérand, France) has undergone the following procedure during the crushing process: the seeds were pre-heated to approximately 115° C., ground/rolled and then pressed in a screw-press where the temperature has reached up to approximately 120° C. Finally, the rapeseed press meal is placed in a cooler to be cooled down to ambient temperature to obtain a rapeseed press flake.

[0338] In order to prove the improvement of the dry thermal treatment according to the present invention on this rapeseed press flake, this one has been ground to obtain a ground rapeseed press flake with a targeted granulometry d.sub.50 around 30 μm, by following the grinding methods described in Example 2, first paragraph of “Preparation of heat treated ground dry material at laboratory scale” (Sample A). A dry content measurement was realized, and the measured value was 96.2%.

[0339] A thermal treatment for 30 minutes at 150° C. in a lab oven was applied on a sample of the rapeseed press flake according to the present invention, by following the grinding and thermal treatment methods described in Example 2, “Preparation of heat treated ground dry material at laboratory scale” (Sample B).

[0340] To check the efficiency of the dry thermal treatment on viscosity, dispersions were prepared by adding from 20% to 40% of the native sample (Sample A) to water. The experiment was reproduced by adding from 20% to 40% of the dry thermally treated sample (Sample B) to water. Prepared dispersions were based on the targeted solid content (accounting of the residual water adsorbed in the material and determined previously with the dry content test) in tap water at ambient temperature in a polypropylene beaker of 100 mL. The dispersions were mixed using a deflocculating blade (10 blades of 49 mm diameter, rod of 7 mm diameter) for two minutes. Viscosity of all these dispersions was measured.

[0341] Results and Discussions

[0342] All viscosity values (in mPa.Math.s) of the two samples in aqueous dispersions are summarized in Table 17:

TABLE-US-00017 TABLE 17 Viscosity of aqueous dispersions prepared from samples A and B Concentration of raw materials in dispersion with water (%) 20% 25% 30% 35% 40% SAMPLE A No treatment 112 380 3100 46000 SAMPLE B 150° C./30 min 25 63 350 2170 40500

[0343] Dispersions prepared from sample B, consisting of water and a dry thermally treated ground rapeseed press flake according to the present invention (dry thermal treatment at laboratory scale), exhibit a dramatic reduction of viscosity in comparison with dispersions prepared from sample A (ground native rapeseed press flake at a similar solid content in the aqueous dispersion). These results show an impact of dry thermal treatment according to the present invention on rapeseed flake which already has undergone a treatment at 120° C. during the crushing process.

EXAMPLE 16

Heat Treated Sunflower Meal Via a Continuous Process

[0344] Equipment & Products

[0345] Products

[0346] Sunflower meal was grinded using Attrition mill (from Atritor Ltd) or Impact Mill (from Hosokawa). Independently of the grinding equipment, the granulometry was the same with a d.sub.50 of 30 μm.

[0347] Thermal Treatment Equipment

[0348] A sterilization reactor was used (FIG. 15). The ground sunflower meal was placed in a buffer hopper 1 which feeds the reactor and the dosage was performed by controlling speed of a feeding screw. The heat treatment was carried out in the horizontal reactor 2 where the product was convoyed thanks an endless screw. The reactor could be warmed using hot air or steam injection 3, a hot air or steam exit 4 being at the end of the reactor. The interest of steam is to avoid or limit product desiccation. The product was heated while it was convoyed through the reactor at a controlled speed. The residence time was between 5 and 30 minutes. The reactor could be also heated by a thermal fluid using a double jacket envelop to ensure a perfect control of temperature for heat treatment (by using thermo-couples placed inside the jacket in contact with the product). An alternative to the usage of thermal fluid is a heating system using Joule effect (electrical heating). In this case, the screw is heated, and it controls product temperature inside the reactor. At the exit 5 the product was cool down using room temperature air.

[0349] From this general description, 3 configurations have been studied: [0350] Configuration n° 1: reactor with a single screw electrically heated; [0351] Configuration n° 2: reactor with a single screw electrically heated and the hot air injection unit; [0352] Configuration n° 3: reactor with double screw system in combination with a heated doubled jacket using oil as a thermal fluid. In this last configuration, the maximal temperature could not exceed 190° C. (limitation linked to the oil thermal stability). The oil circulates inside the screw.

[0353] Viscosity Measurement

[0354] Viscosity was measured with a viscometer EVO expert from FungiLab equipped with a disc spindle (L3). Prior to viscosity measurement, about 100 mL of dispersion, of the desired solid content, was prepared in the adequate beaker to ensure a correct immersion of the spindle until the small mark in the spindle axis. The rotation speed was set depending on the torque scale to reach a torque percentage in between 80% and 40%. With this setting, viscosity measurement higher than 3000 mPa.Math.s cannot be measured. When a dispersion had a viscosity higher than 3000 mPa.Math.s the value “>3000” was reported in the result tables (Tables 18, 19 and 20). The value was recorded after 1 min stabilization time while running the viscometer.

[0355] Results & Discussion

[0356] The results obtained on product viscosity reduction versus the thermal treatment parameter (time and temperature) and configuration (screw electrically heated in combination or not with hot air, double jacket reactor with thermal fluid) are shown below.

[0357] Configuration n° 1

[0358] For this configuration an electrically heated screw was used to apply a thermal treatment on the ground sunflower meal. The flow of material was controlled to get the reactor filled at 20% of its total capacity. Screw temperature was set between 100 to 180° C. with a residence time in between 5 to 30 min. Below 100° C., the temperature was too low to get a significant reduction of viscosity of the dispersion with a reasonable residence time. Above 180° C. it was observed char formation which could affect product performance and could be a risk of fire in the equipment. It was considered a residence time upper than 30 min prohibitive in term of flow rate and operating cost.

[0359] For each condition powder moisture was measured with a moisture analyzer in “atro” mode, right after the thermal treatment. Dispersion of product was prepared at 20 wt % solid content with tap water after product cooled down around room temperature. All results are reported in Table 18.

TABLE-US-00018 TABLE 18 Viscosity of aqueous dispersions depending on the heat treatment conditions of the sunflower meal Screw Flow temperature Residence rate Moisture Viscosity Test (° C.) time (min) (kg/h) (% atro) (mPa .Math. s) Not 6.47 >3000 treated 1-T1 140 20 n/a 0.74 620 1-T4 120 30 12 0.65 840 1-T5 150 30 12 0.20 61 1-T6 160 30 12 0.19 56.5 1-T7 150 20 n/a 0.39 77 1-T8 170 10 40 2.35 1050 1-T10 170 15 30 1.64 650 1-T11 180 10 30 1.56 740 1-T12 180 5 52 2.89 977

[0360] In certain industrial use, a processable dispersion needs to have a viscosity below 500 mPa.Math.s. Thus a temperature of 150° C. appears to be required to get enough viscosity reduction in a reasonable residence time (20 min at 150° C.) in the reactor. Increasing the temperature could help to reduce the treatment time. In this case, the moisture content was dramatically decreased to a value lower than 1% which indicates that the thermal treatment was highly effective. However, a dramatic reduction of residence time was not achieved by increasing the temperature to 170° C. or 180° C. It could be linked to the configuration setting wherein, for these 2 last temperatures, the moisture content remains around 3 to 1%.

[0361] In conclusion, it was demonstrated that the reactor can be used to apply a thermal treatment to ground sunflower meal with a level of efficiency (i.e. reduction of viscosity) equal or even better compared with the lab scale test in an oven. In other word, a continuous process can be used instead of a static process.

[0362] Configuration n° 2

[0363] For configuration n° 2, the same equipment was used. The unique variant in the process is the addition of a hot air injection unit (800° C.) in addition to the heated screw. This additional source of calories may help to accelerate product temperature increases. All results and test conditions were summarized in Table 19.

TABLE-US-00019 TABLE 19 Viscosity of aqueous dispersions depending on the heat treatment conditions of the sunflower meal Screw Flow temperature Residence rate Moisture Viscosity Test (° C.) time (min) (kg/h) (% atro) (mPa .Math. s) 2-T5 120 30 15 1.29 500 2-T6 130 30 15 0.84 253 2-T7 140 30 15 0.61 162 2-T8 150 30 15 0.46 110 2-T9 150 25 21.6 0.44 198 2-T10 160 25 21.6 0.6 150 2-T11 160 20 23.5 0.27 210 2-T12 170 15 30 0.39 400 2-T13 170 18 25 0.48 230

[0364] With this configuration, one can observe a reduction of the minimum temperature required to get an effective reduction of viscosity to 120° C. with 30 min as a residence time. In addition to this, the increase of temperature enabled to significantly reduce the residence time to 15 min at 170° C.

[0365] In conclusion, configuration n° 2, as configuration n° 1, is suitable to apply a thermal treatment to ground sunflower meal using a continuous process. Configuration n° 2 gives a higher level of efficiency allowing to run at a lower temperature than configuration n° 1 or for a lower residence time. In this set of experiments, a flow rate of 30 Kg/h was achieved versus 12K/h for configuration n° 1.

[0366] Configuration n° 3

[0367] In configuration n° 3, the reactor was different in comparison with configuration n° 1 and n° 2. The heating source comes from a double jacket system with an oil heated at 190° C. to warm the screw. In addition, the reactor was equipped with a double screw system (CWR200 from Celsius, NL). The screw was fed to ensure the usage of 70% of the total volume. The screw was too short (2 m) to fully cure the product. Thus, the product was collected at the exit and then re-introduced inside the reactor to simulate longer residence time.

[0368] In this configuration, ground sunflower meal was introduced in the heating reactor. The product was processed in the reactor during 30 min at 190° C. which corresponds to pass n° 1. After it was reintroduced in the reactor which was pass n° 2 and so on.

[0369] After pass n° 3, moisture content of the heat treated sunflower meal and viscosity of the resulting dispersion were measured. All results are reported in Table 20.

TABLE-US-00020 TABLE 20 Viscosity of aqueous dispersions depending on the number of passes Moisture Viscosity Test Pass n° (% atro) (mPa .Math. s) Not treated X 7.43 >3000 6-19 3 1.43 46 6-20 4 0.7 41.5 6-21 5 1.21 51

[0370] After the 3rd pass, a moisture content similar to those of configurations n° 1 and n° 2 was measured (1.5% ATRO); viscosity of a dispersion at 20 wt % solid content has decreased significantly versus the dispersion obtained from non-heat treated ground sunflower meal. Doing a 4.sup.th and a 5.sup.th pass did not provide additional benefits. This configuration n° 3 enables to get dramatic decrease of viscosity until a minimum value around 40 mPa.Math.s. Ground rapeseed meal (Saipol, France) (D.sub.50:30 μm) was also processed with the same configuration. The trends were similar with ground rapeseed meal as previously observed with ground sunflower meal.

CONCLUSION

[0371] In this Example, the possibility to heat treat a ground oilseed meal with a continuous process and to get a significant viscosity reduction once dispersed in water was demonstrated. The type of heating does not impact the quality of these obtained benefits (electric screw, hot air, thermal fluid).