US 2013021 0100A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2013/0210100 A1
BERLIN et al. (43) Pub. Date: Aug. 15, 2013
(54) ORGANOSOLV PROCESS (60) Provisional application No. 61/304.755, filed on Feb.
15, 2010, provisional application No. 61/360,377,
(76) Inventors: Alex BERLIN, Davis, CA (US); filed on Jun. 30, 2010.
Mikhail Y. Balakshin, North Vancouver
(CA); Raymond Ma, N. Vancouver Publication Classification
(CA); Vera Maximenko Gutman,
Davis, CA (US); Darwin Ortiz, Delta (51) Int. Cl.
(CA) CI2P I/00 (2006.01)
(52) U.S. Cl.
(21) Appl. No.: 13/584,697 CPC ........................................ CI2P I/00 (2013.01)
USPC ........................................... 435/165; 435/267
(22) Filed: Aug. 13, 2012 (57) ABSTRACT
Related U.S. Application Data The present disclosure provides an organosolv process. The
present process comprises treating a lignocellulosic biomass
(63) Continuation of application No. PCTACA2O11/ in the presence of a solvent and under certain conditions to
000183, filed on Feb. 15, 2011. separate at least a part of the lignin from the biomass.
Patent Application Publication Aug. 15, 2013 Sheet 1 of 5 US 2013/0210100 A1

?y () () O > 1) - > -- O & D -

- a
L
D
c
- d
O
will
CfO
c
S

a.
Patent Application Publication Aug. 15, 2013 Sheet 3 of 5 US 2013/0210100 A1

FIG 3

Cacuation of S10005865 TCT

100
Y-105.3616XI(40.36683+X); r-0.9971
TCT168.6 h

468O
2O

O 20 40 60 80 100 20
Time, h
Patent Application Publication Aug. 15, 2013 Sheet 4 of 5 US 2013/0210100 A1

FIG. 4

Calculation of 14(1) TCT

100
Y=105.36762"X1(29.03843-X); r=0.99769
TCT1215 h

4.68O
2O

0 20 40 60 80 100 120
Time, h
Patent Application Publication Aug. 15, 2013 Sheet 5 of 5 US 2013/0210100 A1

FGS

Calculation of 10005636 TCT

00
Y-98.13273*X/(18,18131-X); r’-0.98916
TCT 17.5 h
8O

6O

4.O

2O

0 20 40 60 80 100 120
Time, h
US 2013/021 0 1 00 A1 Aug. 15, 2013

ORGANOSOLV PROCESS of the invention will be apparent to those of ordinary skill in

the art upon review of the following description of specific
0001. This application is a continuation of PCT/CA2011/ embodiments of the invention.
000183, filed Feb. 15, 2011; which claims the priority of U.S.
Provisional Application Nos. 61/304.755, filed Feb. 15, 2010, BRIEF DESCRIPTION OF THE DRAWINGS
and 61/360,377, filed Jun. 30, 2010. The contents of the
above-identified applications are incorporated herein by ref 0010 FIG. 1 shows a typical Lignol R lignin (AlcellR)
erence in their entirety. organosolv process;
TECHNICAL FIELD 0011 FIG. 2 shows the dependence of lignin & glucose
yields on solids content (L: W Ratio) at 2% acid on aspen
0002 This disclosure relates to an organosolv process. wood, 50% EtOH in liquor, 120 min cooking time, 165° C.
This disclosure further relates to the lignins, uses, apparatus, cooking temperature;
and the like. 0012 FIGS. 3, 4 and 5 shows the time-to-conversion target
for various biomass samples.
BACKGROUND
0003 For environmental, economic, and resource security DETAILED DESCRIPTION
reasons, there is an increasing desire to obtain energy and 0013 The present disclosure provides an organosolv pro
material products from bio-renewable resources and particu cess. Organsolv processes are well known in the art. See, for
larly from “waste' and/or non-food biomass feedstocks. The example, U.S. Pat. No. 4,100,016; U.S. Pat. No. 4,764,596:
various chemical components within typical biomass can be U.S. Pat. No. 5,681,427; U.S. Pat. No. 7,465,791; US Patent
employed in a variety of ways. In particular, the cellulose and Application 2009/01 18477; US Patent Application 2009/
hemicellulose in plant matter may desirably be separated out 0062516; US Patent Application 2009/00669550; or U.S. Pat.
and fermented into fuel grade alcohol. And the lignin com No. 7,649,086.
ponent, which makes up a significant fraction of species Such
as trees and agricultural waste, has huge potential as a useful 0014 Four major “organosolv’ pulping processes have
Source of aromatic chemicals for numerous industrial appli been tested on a trial basis. The first method uses ethanol/
cations. However, most separation techniques employed by water pulping (aka the Lignol R (AlcellR) process); the sec
industry today are too harsh and chemically alter the lignin ond method uses alkaline Sulphite anthraquinone methanol
component during separation to the point where it is no longer pulping (aka the ASAM process); the third process uses
acceptable for use in many of these potential applications. methanol pulping followed by methanol, NaOH, and
0004 Organosolv extraction processes can be used to anthraquinone pulping (aka the "Organocell' process); the
separate lignin and other useful materials from biomass. Such fourth process uses acetic acid/hydrochloric acid or formic
processes can be used to capitalize on the value from multiple acid pulping (aka the "Acetosolv” and “Formacell pro
components in the biomass. Organosolv extraction processes cesses).
however typically involve extraction at higher temperatures 0015. A description of the Lignol R AlcellR) process can be
and pressures with a volatile solvent than other industrial found, for example, in U.S. Pat. No. 4,764,596 or Kendall Pye
methods and thus are generally more complex and expensive. and Jairo H. Lora, The AlcellTM Process, Tappi Journal,
While large scale commercial viability had been demon March 1991, pp. 113-117 (the documents are herein incorpo
strated decades ago from a technical and operational perspec rated by reference). The process generally comprises pulping
tive, organosolv extraction has not, to date, been widely or pre-treating a fibrous biomass feedstock with primarily an
adopted. ethanol/water solvent solution under conditions that include:
(a) 60% ethanol/40% water (W/W), (b) a temperature of
SUMMARY about 180° C. to about 210°C., and (c) pressure of about 20
0005. The present disclosure provides an organosolv pro atm to about 35 atm. Derivatives of native lignin are fraction
cess. The present process comprises treating alignocellulosic ated from the biomass into the pulping liquor which also
biomass in the presence of a solvent and under certain con receives solubilised hemicelluloses, other carbohydrates and
other components such as resins, phytosterols, terpenes,
ditions to separate at least a part of the lignin from the biom organic acids, phenols, and tannins. Organosolv pulping
ass. For example, the present process may be a biorefinery liquors comprising the fractionated derivatives of native lig
process. As used herein, the term “biorefining refers to the nin and other components from the fibrous biomass feed
co-production of bio-based products (e.g. lignin derivatives), stocks, are often called “black liquors'. The organic acid and
fuel (e.g. ethanol), and energy from biomass. other components released by organosolv pulping signifi
0006. As used herein, the term “organosolv’ refers to bio cantly acidify the black liquors to pH levels of about 5 and
refinery processes wherein the biomass is Subject to an extrac lower. After separation from the pre-treated lignocellulosic
tion step using an organic Solvent at an elevated temperature. biomass or pulps produced during the pre-treatment process
0007 As used herein, the term “native lignin refers to (e.g. pulping process), the derivatives of native lignin are
lignin in its natural state, in plant material. recovered from the black liquor by flashing followed by dilu
0008. As used herein, the terms “lignin derivatives” and tion with acidified cold water and/or stillage which will cause
"derivatives of native lignin” refer to lignin material extracted most of the fractionated derivatives of native lignin to pre
from lignocellulosic biomass. Usually, such material will be cipitate thereby enabling their recovery by standard solids/
a mixture of chemical compounds that are generated during liquids separation processes. Various disclosures exemplified
the extraction process. by U.S. Pat. No. No. 7.465,791 and PCT Patent Application
0009. This summary does not necessarily describe all fea Publication No. WO 2007/129921, describe modifications to
tures of the invention. Other aspects, features and advantages the Lignol R Alcell R organosolv.
US 2013/021 0 1 00 A1 Aug. 15, 2013

0016 Organosolv processes, particularly the LignolR) 0024. Embodiments of the present disclosure offer sur
Alcell R process, can be used to separate highly purified lig prisingly highlignin yields which increases the value deriv
nin derivatives and other useful materials from biomass. Such able from the lignin stream of a particular process and may
processes may therefore be used to exploit the potential value also reduce the amount of non-recovered lignin contaminat
of the various components making up the biomass. ing product streams from the process.
0017 Organosolv extraction processes however typically 0025 Embodiments of the present disclosure offer pre
involve extraction at higher temperatures and pressures with treated Solids (“pulps') with Surprisingly good enzymatic
a volatile solvent compared to other industrial processes and hydrolyzability. This characteristic increases the pulps reac
thus are generally considered to be more complex and expen tivity to enzymes and, hence, reduces the amount of enzyme
sive. For example, when the processes are run at higher pres needed for converting the pulp to Sugars and Subsequently to
Sures (~25-30 bar) capital costs can increase due to the neces ethanol or other chemicals.
sity of using more robust equipment. In addition, the 0026. Embodiments of the present disclosure offer sur
necessity of heating the biomass to high temperatures prisingly high yields of glucose.
requires extra expense in terms of energy input leading to 0027. The present invention provides an organosolv pro
increases in operating costs. cess, said process comprising:
0018 Moreover, organosolv extraction processes can 0028 (a) pretreating (e.g. pulping) alignocellulosic bio
result in the production of self-precipitated lignins or lignins mass with an organic solvent to form a pulp comprising
with poor solubility in the cooking liquor (SPLs), particularly cellulose and an extraction liquor comprising lignin deriva
when using softwood biomass but also when other types of tives;
biomass is used. SPLS can attach to metal Surfaces causing
equipment to be fouled and are difficult to remove. 0029 (b) separating the cellulosic pulp from the extraction
0019. In order to improve the commercial viability of liquor, and
organosolv processes it is desirable to keep capital and oper 0030 (c) recovering at least a portion of the extracted
ating costs low while maximizing the potential revenue compounds from the extraction liquor.
streams. For example, the cost of the enzymes used to convert 0031. At least a portion of the cellulosic pulp may be
the cellulose-rich pulp to mono- and/or oligosaccharides converted into carbohydrates, ethanol, or other chemicals.
which can then be fermented into biofuels such as ethanol and 0032. The pretreatment step (a) of the present process can
n-butanol, or bio-based chemicals such as Xylitol and other be operated at pressures of about 24 bar or less. For example,
Sugar-alcohols, succinic acid and other organic acids etc., about 23 bar or less, about 22 bar or less, about 21 bar or less.
represents a significant operating cost and, therefore, it would 0033. The biomass/solvent mixture of pretreatment step
be advantageous to reduce the amount of enzymes needed. (a) of the present process may be heated to a temperature of
This may beachieved by, for example, improving the “hydro from about 130°C. or greater, about 132°C. or greater, about
lyzability” of the pulp. Also, recovered lignin derivatives 134°C. or greater, about 136°C. or greater, about 138°C. or
represent a source of high-value chemicals and, therefore, it greater, about 140° C. or greater, about 142°C. or greater,
would be advantageous to increase the yield of Such Sub about 144°C. or greater, about 146°C. or greater, about 148
stances. Moreover, the production of less desirable by-prod C. or greater, about 150° C. or greater, about 152° C. or
ucts, for example acetic acid, should be reduced. greater, about 154°C. or greater.
0020 Surprisingly, it has been found that organosolv pro 0034. The biomass/solvent mixture of pretreatment step
cesses operated within relatively narrow ranges of process (a) of the present process may be heated to a temperature of
conditions offer significant advantages in terms of commer from about 170° C. or less, 168° C. or less, 166° C. or less,
cial viability. For example, processes according to the present about 165° C. or less.
disclosure may offer improved glucose yield, lignin yield, 0035. For example, the biomass/solvent mixture of pre
and/or reduced production of acetic acid. treatment step (a) of the present process may be heated to a
0021. The present disclosure offers a commercially attrac temperature of from about 155° C. to about 170° C.
tive organosolv process which operates at significantly lower
temperature and pressure than typical for organosolv biore 0036. The biomass/solvent mixture of pretreatment step
fining with consequent savings in capital, operating, and/or (a) of the present process may be kept at the elevated tem
energy expenditure. perature for about 45 minutes or more, about 50 minutes or
0022. Embodiments of the present process demonstrate more, about 55 minutes or more, about 60 minutes or more,
significantly less fouling than seen in prior art organosolv about 65 minutes or more, about 70 minutes or more, about 75
processes. For example, when the present process utilizes minutes or more, about 80 minutes or more, about 95 minutes
softwood feedstock there is a marked reduction in the amount or more, about 100 minutes or more.
of SPLs seen. A reduction in the amount of SPLs can result in 0037. The biomass/solvent mixture of pretreatment step
lower equipment fouling. This offers the possibility of an (a) of the present process may be kept at the elevated tem
improved commercial scale organosolv plant that has the perature for about 200 minutes or less, about 195 minutes or
ability to process softwood and other types of biomass that less, about 190 minutes or less, about 180 minutes or less,
suffer from problems with SPLs. about 170 minutes or less, about 160 minutes or less, about
0023 Typical organosolv processes such as Lignol's(R) 150 minutes or less, about 140 minutes or less, about 130
minutes or less.
Alcell(R) process, generally recover around 60% of the theo
retical maximum lignin. The remaining lignin is generally 0038. For example, the biomass/solvent mixture of pre
degraded and ends up as a waste residue. This non-recovered treatment step (a) of the present process may be kept at the
fraction can be toxic to microorganisms and can contaminate elevated temperature for about 100 to about 140 minutes.
certain of the product streams reducing their processability by 0039. The solvent mixture of pretreatment step (a) of the
microorganisms and/or value. present process may comprise about 40 wt.% or more, about
US 2013/021 0 1 00 A1 Aug. 15, 2013

42% or more, about 44% or more, about 46% or more, about Blackbean; Blackwood; Bocote; Boxelder; Boxwood; Bra
48% or more, about 50% or more, organic solvent such as Zillwood: Bubinga; Buckeye (e.g. Aesculus hippocastianum,
ethanol. Aesculus glabra, Aesculus flava/Aesculus octandra); Butter
0040. The solvent mixture of pretreatment step (a) of the nut; Catalpa; Cherry (e.g. Prunus serotina, Prunus pennsyl
present process may comprise about 70 wt.% or less, about vanica, Prunus avium); Crabwood; Chestnut; Coachwood;
68% or less, about 66% or less, about 64% or less, about 62% Cocobolo; Corkwood; Cottonwood (e.g. Populus balsam
or less, about 60% or less, about 58% or less, about 56% or ifera, Populus deltoides, Populus Sargentii, Populus hetero
less, organic solvent Such as ethanol. phylla); Cucumbertree; Dogwood (e.g. Cornus florida, Cor
0041. For example, the solvent mixture of pretreatment nus nuttallii), Ebony (e.g. Diospyros kurzii, Diospyros
step (a) of the present process may comprise about 45 wt.% melanida, Diospyros crassiflora); Elm (e.g. Ulmus ameri
to about 60%, about 50% to about 55% organic solvent such cana, Ulmus procera, Ulmus thomasii, Ulmus rubra, Ulmus
as ethanol. glabra); Eucalyptus; Greenheart; Grenadilla; Gum (e.g.
0042. The solvent mixture of pretreatment step (a) of the Nyssa sylvatica, Eucalyptus globulus, Liquidambar styraci
present process may have a pH of from about 1.5 or greater, flua, Nyssa aquatica); Hickory (e.g. Carya alba, Carya gla
about 1.6 or greater, about 1.7 or greater, about 1.8 or greater, bra, Carya ovata, Carya laciniosa); Hornbeam; Hophorn
about 1.9 or greater, about 2.0 or greater, about 2.1 or greater, beam; Ipe; Iroko: Ironwood (e.g. Bangkirai, Carpinus
about 2.2 or greater, about 2.3 or greater, about 2.4 or greater, caroliniana, Casuarina equisetifolia, Choricbangarpia sub
about 2.5 or greater. The solvent mixture of pretreatment step argentea, Copaifera spp., Eusideroxylon Zwageri, Guaiacum
(a) of the present process may have a pH of from about 3.0 or officinale, Guaiacum Sanctum, Hopea odorata, Ipe, Krugio
lower, about 2.9 or lower, about 2.8 or lower, about 2.7 or dendron ferreum, Lyonothamnus lyonii (L. floribundus),
lower. For example, the solvent mixture of pretreatment step Mesua ferrea, Olea spp., Olneya tesota, Ostrya virginiana,
(a) of the present process may have a pH of from about 2.4 to Parrotia persica, Tabebuia serratifolia); Jacaranda; Jotoba;
about 2.8. For example, from about 2.5 to about 2.7. For the Lacewood; Laurel; Limba; Lignum Vitae; Locust (e.g. Rob
sake of clarity, as used in this context we refer to the pH of the inia pseudacacia, Gleditsia triacanthos); Mahogany; Maple
mixture before elevating the temperature i.e. before the (e.g. Acer Saccharum, Acer nigrum, Acer negundo, Acer
cook. rubrum, Acer saccharinum, Acer pseudoplatanus); Meranti;
0043. From about 1.5% or greater, 1.7% or greater, 1.9% Mpingo; Oak (e.g. Quercus macrocarpa, Quercus alba,
or greater, 2% or greater, by weight, of acid (based on dry Quercusstellata, Quercus bicolor, Quercus virginiana, Ouer
weight wood) may be added to the biomass. From about 3% cus michauxi, Quercus prinus, Quercus muhlenbergii, Ouer
or lower, 2.7% or lower, 2.5% or lower, by weight, of acid cus chrysolepis, Quercus lyrata, Quercus robur, Quercus
(based on dry weight wood) may be added to the biomass. petraea, Quercus rubra, Quercus velutina, Quercus laurifo
0044) The weight ratio of liquor to biomass in the pretreat lia, Quercus falcata, Quercus migra, Quercus phellos, Ouer
ment step (a) may be from about 10:1 to about 4:1, about 9:1 cus texana); Obeche: Okoumé: Oregon Myrtle; California
to about 5:1, about 8:1 to about 6:1. Bay Laurel; Pear; Poplar (e.g. P. balsamifera, P. nigra, Hybrid
0045. The pretreatment step (a) of the present process may Poplar (PopulusXCanadensis)); Ramin; Red cedar, Rose
generate pretreated biomass solids with Time-to-Conversion wood; Sal; Sandalwood; Sassafras; Satinwood; Silky Oak;
Target (TCT) equal to about 120h or less, about 110h or less, Silver Wattle: Snakewood: Sourwood; Spanish cedar; Ameri
about 100 horless, about 90 horless, about 80 horless, about can Sycamore; Teak, Walnut (e.g. Juglans nigra, Juglans
75 h or less, about 60 h or less, about 40 h or less. The regia); Willow (e.g. Salix nigra, Salix alba); Yellow poplar
pretreatment step (a) may generate pretreated biomass solids (Liriodendron tulipifera); Bamboo: Palmwood; and combi
with an Overall Glucan Conversion (OGC) of about 50% or nations/hybrids thereof.
higher, about 65% or higher, about 70% or higher, about 75% 0049. For example, hardwood feedstocks for the present
or higher, about 80% or higher, about 85% or higher. invention may be selected from Acacia, Aspen, Beech, Euca
0046. The present organic solvent may be selected from lyptus, Maple, Birch, Gum, Oak, Poplar, and combinations/
any suitable solvent. For example, aromatic alcohols such as hybrids thereof. The hardwood feedstocks for the present
phenol, catechol, and combinations thereof, short chain pri invention may be selected from Populus spp. (e.g. Populus
mary and secondary alcohols, such as methanol, ethanol, tremuloides), Eucalyptus spp. (e.g. Eucalyptus globulus),
propanol, and combinations thereof. For example, the Solvent Acacia spp. (e.g. Acacia dealbata), and combinations/hy
may be a mix of ethanol & water. brids thereof.
0047. The present process may utilize any suitable ligno 0050 Softwood feedstocks include Araucaria (e.g. A. cun
cellulosic feedstock including hardwoods, Softwoods, annual ninghamii, A. angustifolia, A. araucana); Softwood Cedar
fibres, energy crops, municipal waste, and combinations (e.g. Juniperus virginiana, Thuja plicata, Thuja Occidentalis,
thereof. Chamaecyparis thyoides Callitropsis nootkatensis); Cypress
0048 Hardwood feedstocks include Acacia; Afzelia: Syn (e.g. Chamaecyparis, Cupressus Taxodium, Cupressus ari
sepalum duloificum, Albizia; Alder (e.g. Alnus glutinosa, zonica, Taxodium distichum, Chamaecyparis obtusa,
Alnus rubra); Applewood; Arbutus; Ash (e.g. F. nigra, F. Chamaecyparis lawsoniana, Cupressus Semperviren); Rocky
quadrangulata, F. excelsior, F. pennsylvanica lanceolata, F. Mountain Douglas fir; European Yew; Fir (e.g. Abies bal
latifolia, F. profinda, F. americana); Aspen (e.g. P. grandi samea, Abies alba, Abies procera, Abies amabilis); Hemlock
dentata, P tremula, P tremuloides); Australian Red Cedar (e.g. Tsuga Canadensis, Tsuga mertensiana, Tsuga hetero
(Toona ciliata): Ayna (Distenonanthus benthamianus); phylla); Kauri, Kaya; Larch (e.g. Larix decidua, Larix
Balsa (Ochroma pyramidale); Basswood (e.g. T. americana, kaempferi, Larix laricina, Larix Occidentalis); Pine (e.g.
T. heterophylla); Beech (e.g. F. Sylvatica, F. grandifolia); Pinus nigra, Pinus banksiana, Pinus contorta, Pinus radiata,
Birch; (e.g. Betula populifolia, B. nigra, B. papyrifera, B. Pinus ponderosa, Pinus resinosa, Pinus Sylvestris, Pinus
lenta, B. alleghaniensis/B. lutea, B. pendula, B. pubescens); strobus, Pinus monticola, Pinus lambertiana, Pinus taeda,
US 2013/021 0 1 00 A1 Aug. 15, 2013

Pinus palustris, Pinus rigida, Pinus echinata); Redwood; these examples are for illustrative purposes only, and should
Rimu, Spruce (e.g. Picea abies, Picea mariana, Picea not be used to limit the scope of the present invention in any
rubens, Picea sitchensis, Picea glauca); Sugi, and combina a.
tions/hybrids thereof.
0051. For example, softwood feedstocks which may be EXAMPLES
used herein include cedar; fir, pine; spruce; and combina 0058. The following examples are intended to be exem
tions/hybrids thereof. The softwood feedstocks for the plary of the invention and are not intended to be limiting.
present invention may be selected from loblolly pine (Pinus
taeda), radiata pine, jack pine, spruce (e.g., white, interior, Example 1
black), Douglas fir, Pinus silvestris, Picea abies, and combi
nations/hybrids thereof. The softwood feedstocks for the 0059 All the modeling work was performed with the help
present invention may be selected from pine (e.g. Pinus of two software packages: Microsoft Excel 2007 & MatLab
radiata, Pinus taeda); spruce; and combinations/hybrids Version 7.7.0.471 (R2008b) with Model-Based Calibration
thereof. Toolbox Version3.5& the CAGE Optimization Module (The
0.052 Annual fibre feedstocks include biomass derived MathWorks, Inc., MA, USA).
from annual plants, plants which complete their growth in one 0060. The aspen chips used for the optimization were pro
growing season and therefore must be planted yearly. duced by Econotech after debarking and splitting logs
Examples of annual fibres include: flax, cereal straw (wheat, sourced from a local BC forest. Validation of the found opti
barley, oats), Sugarcane bagasse, rice Straw, corn stover, corn mal region was performed with aspen chips Supplied by West
cobs, hemp, fruit pulp, alfalfa grass, esparto grass, Switch Fraser, Alberta and screened at Lignol by Pilot Plant Opera
grass, and combinations/hybrids thereof. Industrial residues tions.
like corn cobs, fruit peals, seeds, etc. may also be considered 0061 Enzymatic hydrolysis was run at 50 g scale at 16%
annual fibres since they are commonly derived from annual solids, 120h, 150 rpm, pH 5.0, CellicCTec2 loaded at 12 mg/g
fibre biomass such as edible crops and fruits. For example, the glucan. Samples were taken after 24h hydrolysis but here for
annual fibre feedstock may be selected from wheat straw, simplicity we will report only yields after 120 h hydrolysis.
corn Stover, corncobs, Sugarcane bagasse, and combinations/ This experimental design has proven to be representative of
hybrids thereof. what one can see at larger scale (4-L & 20-L fermentor Scale).
0053. It is contemplated that any embodiment discussed in 0062. Thirty eight sets of five process variables (Table 1)
this specification can be implemented or combined with were selected to run the optimization experiments and the
respect to any other embodiment, method, composition or results were used to build the models (Table 3).
aspect of the invention, and vice versa. 0063 Results & Discussion
0054. Unless defined otherwise, all technical and scien 0064. The produced models showed that one can find pre
tific terms used herein have the same meaning as is commonly treatment conditions for Aspen biomass where the Lignin
understood by one of ordinary skill in the art to which this Yield is higher than 80% and the Glucose Yield is higher than
invention belongs. Unless otherwise specified, all patents, 85%. In all studied conditions the operating pressure was
applications, published applications and other publications around 16 bar or lower.
referred to herein are incorporated by reference in their 0065 Conclusions
entirety. If a definition set forth in this section is contrary to or 0066. The optimum conditions for aspen lignin yield and
otherwise inconsistent with a definition set forth in the pat glucose yield (-80% or higher theoretical yields) lies
ents, applications, published applications and other publica between 155 and 165° C., -50-55%. EtOH, 120-180 min
tions that are herein incorporated by reference, the definition cooking time, 2.0-2.5% acid at a fixed L: Wratio of 8:1 to 7:1.
set forth in this section prevails over the definition that is Any combination of these conditions yields operating pres
incorporated herein by reference. Citation of references sures around or below 16 bar. Decrease of L: Wratio (increase
herein is not to be construed nor considered as an admission of% solids) is beneficial and leads to increase glucose and
that Such references are prior art to the present invention. lignin yields under certain conditions such as the ones
0055. Use of examples in the specification, including described in FIG. 2.
examples of terms, is for illustrative purposes only and is not
intended to limit the scope and meaning of the embodiments TABLE 1
of the invention herein. Numeric ranges are inclusive of the
numbers defining the range. In the specification, the word Sets of process variables selected to run the optimization experiments
“comprising is used as an open-ended term, Substantially Acid Time Temperature Ethanol Solids L:W
equivalent to the phrase “including, but not limited to.” and i % wt. min o C. % wt. % :1
the word “comprises' has a corresponding meaning. 1: 2.00 105 148 55 1S.O 5.7
0056. The invention includes all embodiments, modifica 2: 2.50 143 139 48 12.5 7.0
tions and variations substantially as hereinbefore described 3: 1...SO 68 1S6 63 17.5 4.7
and with reference to the examples and figures. It will be 4:
5*
1.38
1.63
133
114
158
145
53
42
10.6
11.9
8.4
7.4
apparent to persons skilled in the art that a number of varia 6* 2.06 166 144 63 10.3 8.7
tions and modifications can be made without departing from 7: 1.69 175 151 50 17.2 4.8
the scope of the invention as defined in the claims. Examples 8:8 2.44 82 155 62 10.9 8.1
of such modifications include the substitution of known 9* 2.00 112 152 55 13.1 6.6
10* 1.41 168 152 57 12.7 6.9
equivalents for any aspect of the invention in order to achieve 11: 2.50 145 143 48 11.6 7.6
the same result in Substantially the same way. 12: 2.28 140 150 63 12.0 7.3
0057 The present invention will be further illustrated in 13: 1...SO 78 161 63 14.6 5.8
the following examples. However it is to be understood that
US 2013/021 0 1 00 A1 Aug. 15, 2013

TABLE 1-continued TABLE 3-continued

Sets of process variables selected to run the optimization experiments Lignin Yield, Glucose Yield, and Washed Pulp Yields Models
Acid Time Temperature Ethanol Solids L:W Time + 0.003185.002 * Time * EtOH + 0.03481116 * Time Acid
i % wt. min o C. % wt. % :1 O.O4457228 * Time * Solids - O.O39691.31 * EtOH* EtOH
0.07047815* EtOH* Solids (r2 = 0.705)
14: .78 103 59 55 4.5 5.9 Glucose Yield (%) = -62.07805 + 2.045008 * Time - 186.731 *
15: 2.53 121 37 59 O.8 8.3 Acid + 32.86724* Solids - 0.007077812 * Temp * Time +
16* 97 145 49 43 O.S 8.6 0.02055919 * Temp * EtOH + 0.7270062 * Temp* Acid - 0.1413414*
17: 2.75 128 39 66 3.9 6.2 Temp * Solids - 0.005416981 * Time * EtOH - 0.05171966 * Time *
18:8 .75 62 57 51 O.9 8.2 Solids - 0.4617057 * EtOH* Acid - 0.291.3332 * EtOH* Solids -
19* 59 98 43 53 1.1 8.O 8.3OO157* Acid Acid - 1758.393 Acid Solids - 0.3140979 *
20* 25 95 48 59 5.4 5.5 Solids * Solids (r2 = 0.858)
21: 34 79 64 41 2.3 7.1 Washed Pulp Yield (%) = -15.8281 + 0.621621 * EtOH
22* 2.83 92 39 63 3.8 6.2 5.53252* Acid + 15.7276* Solids + 0.00179991 * Temp * Temp
23: 2.25 61 66 44 2.4 7.1 0.0821519 * Temp * Solids + 0.00062543 * Time * Time
24: S8 11 52 67 O.1 8.9 O.OO132139* Time * EtOH. O.O23O2O2 * Time Acid - 0.0118592 *
25: 2.08 73 61 59 2.6 7.0 Time * Solids - 0.0444829 * EtOH * Solids (r2 = 0.901)
26* 88 70 36 61 S.O 5.7
27: 2O 45 59 69 2.0 7.4
28:8 2.45 76 37 65 3.2 6.6
29* 2.88 O3 S4 46 2.0 7.4 Example 2
30: 52 62 40 60 5.4 5.5 0067. Reactivity of Biomass Samples
31:
32:
2.27
2.38
69
70
44
45
49
68
1.6
3.5
7.6
6.4
0068 “Time-to-Conversion-Target” (TCT, h) is a metric
33: 2.89 53 34 51 1.O 8.1 which characterizes biomass reactivity and it is defined as the
34: 89 78 51 66 6.O 5.2 time in hours required to enzymatically convert 85% of the
35: 2.14 72 55 47 2.3 7.2 total glucan in a pretreated biomass sample to monomeric
36* 38 36 63 53 O.S 8.5 glucose under the following reaction conditions:
37:
38:
.64
2.89
59
76
64
66
55
69
4.8
7.5
5.8
4.7
0069 12 mg protein/g glucan of the state-of-the-art
Min 2O 45 34 41 O.1 4.7
enzyme CellicCTec2 (Novozymes North America Inc., Fran
Max 2.89 76 66 69 7.5 8.9
klinton, N.C., USA). The protein content in the preparation is
determined by the Pierce(R) Micro BCA Protein Assay Kit
(Thermo Fisher Scientific Inc., Waltham, Mass., USA) in
absence of interfering compounds or the enzyme protein con
TABLE 2 tent value is Supplied by the enzyme manufacturer,
(0070) 50 g total reaction weight;
Output boundaries of dependent process variables 0071. 16% total pretreated biomass solids in reaction;
Lignin Yield Glucose Yield Washed Pulp Yield (0072 pH 5.0, 0.1 M sodium citric buffer prepared in
% % % bd wood deionized water;
Min 51.5 70.2 42.8
(0073 0.50 ppm antibiotic LactrolR;
Max 85.1 87.5 55.8
0074 50° C.;
0075 150 rpm mixing rate in an air incubator;
(0076 Five Zr beads per flask (Cat. No. 08-412-15C,
Grinding Media for Ball Mills (Zirconia), O.D.xH 13x13
TABLE 3 mm);
0077 250-mL total volume of a sterilized by autoclaving
Lignin Yield, Glucose Yield, and Washed Pulp Yields Models glass Erlenmeyer reaction flask
Lignin Yield (%) = -146.0292 + 27.99547 * Solids + 0.03120071 * 0078. The flask must be plugged with a foam plug cover by
Temp * EtOH - 0.1121524* Temp * Solids + 0.0015453 * Time * an aluminum foil to avoid evaporation or equivalent. The
glucose released is measured chromatographically.
TABLE 4

Comparison of biomass reactivity (TCT, h) between three differently pretreated

aspen samples

Biomass P Acid Time EtOH Solids L:W TCT

Sample (bar) (% wt) pH (min) T (C.) (% wt) (% wt) Ratio (h)

S1 OOOS865 9.7 120 2.20 45 159 69 12 7.40 168.6

28(1)
14(1) 12.8 1...SO 2.02 78 161 63 15 5.85 121.5
S1 OOOS636 11.0 18O 1.90 103 159 55 15 5.90 117.5
15(1)
US 2013/021 0 1 00 A1 Aug. 15, 2013

0079. The pretreated biomass sample S10005636 15(1) I0081 “Maximum Operating Pressure” (P. bar) is
shows the highest reactivity with the shortest time (117.5 h) defined as the maximum operating pressure reached during
required to achieve the target (85% glucan-to-glucose con the biomass pretreatment stage. In the case of the present
version) while the sample S10005865 28(1) shows the lowest invention this value is around 16 bar or lower.
reactivity with a 168.6hTCT. The TCT values are calculated I0082 “Best Pretreated Biomass” (BPB) is defined as the
by extra- or intrapolation using the experimental hyperbolic pretreated biomass produced under Paround or lower than
functions Glucan-to-Glucose Conversion (%) vs. Time (h) 16 bar which shows the lowest TCT and the highest OGC with
(FIGS. 3-5). These hyperbolic functions are typical of enzy the highest lignin yield. The lignin yield must be considered
matic hydrolysis reactions. for economic reasons but it does not necessarily impacts
0080 “Overall Glucose Conversion” (OGC, % total glu biomass reactivity.
cose in raw biomass) is a metric which provides the total I0083. In the case of the three compared pretreated aspen
glucose recovered from the pretreated solids in fermentable samples the BPB is the sample S10005636 15(1) since it
monomeric form and it integrates both the glucose recovery showed the highest OGC and the lowest TCT while the maxi
yield after biomass pretreatment (PGY Pretreatment Glu mum operating pressure (11 bar) was kept well below the
cose Yield) and the glucose hydrolysis yield after enzymatic allowed maximum of 16 bar.
hydrolysis (HGY Hydrolysis Glucose Yield). The OGC is
calculated as follows: Example 3
OGC (%)=Recovered Glucose. After Pretreatment
per 100 g Pretreated Raw Material (g)*HGY I0084 Various types of feedstock were processed in the
(%) pilot plant facility at Lignol Innovations Inc, Burnaby,
TABLE 5

Overall Glucose Conversion (OGC, % total glucose in raw biomass)

yields of three differently pretreated aspen samples

Biomass P, Acid Time EtOH Solids L:W OGC

Sample (bar) (% wt) pH (min) T (C.) (% wt) (% wt) Ratio (%)

S1 OOOS865 9.7 1.20 2.2O 45 159 69 12 7.40 78.17

28(1)
14(1) 12.8 1...SO 2.02 78 161 63 15 5.85 76.57
S1 OOOS636 11.0 18O 1.90 103 159 55 15 5.90 79.11
15(1)

Canada. Numerous runs were performed (Table 6). The

resultant pulp glucan to ethanol conversion was 80% or
greater. In addition, no significant issues were observed with
SPLS.

TABLE 6

Pilot Plant Cooking Conditions/Results

Best attained
Pulp
Primary Acid Glucan
Ext. Loading Ethanol
Feed No. of Time (% OD Temp. Pressure Conversion
Ext. Stock cooks LW (min) wood) (° C.) (kPa) (%)

A. Aspen 43 7-10 120 2-2.5 16S 2100 81

Alder 51 7-10 120 2-2.5 16S 2100 81
BKLP* 83 7-10 120 2.5-3.5 16S 2100 8O
B Aspen 181 7-8 120 2-2.5 16S 2100 81
Alder 13 7-8 120 2-2.5 16S 2100 81
BKLP* 13 7.5-10 120 2.5-3.5 16S 2100 8O

*Beetle Killed Logpole Pine

US 2013/021 0 1 00 A1 Aug. 15, 2013

1. An organosolv process for treating a lignocellulosic 3. The process of claim 1 or 2 wherein the pressure in the
biomass comprising: reaction vessel is about 21 bar or less.
a. Adding the biomass to a reaction vessel and exposing the 4. The process of claim 1 or 2 wherein the elevated tem
biomass to a solvent wherein: perature of step (b) is from about 160° C. to about 170° C.
i. the ratio of solvent to biomass is from about 10:1 to 5. The process of claim 1 or 2 wherein the elevated tem
about 4:1; perature of step (b) is maintained for about 100 minutes to
ii. the solvent comprises from 40 to 60% w/w ethanol: about 140 minutes.
iii. from about 1.5% to about 2.5% (based on dry weight 6. The process of claim 1 or 2 wherein the solvent com
wood) of an acid is added; prises from 50% to 60% w/w ethanol.
b. Elevating the temperature of the biomass/solvent mix 7. The process of claim 1 or 2 wherein from about 2% to
ture to from about 140° C. to about 170° C. for a total about 2.5% (based on dry weight wood) of an acid is added.
period of from about 50 minutes to about 200 minutes to 8. The process of claim 1 or 2 wherein the ratio of solvent
form a pulp and an extraction liquor said liquor compris to biomass is from about 7:1 to about 5:1.
ing extracted derivatives of native lignin; 9. The process of claim 1 or 2 wherein the biomass com
c. Recovering at least a portion of the extraction liquor; prises softwood feedstock.
d. Recovering at least a portion of the pulp; and 10. The process of claim 1 or 2 wherein the biomass com
wherein the pressure in the reaction vessel is less about 22 prises hardwood feedstock.
bar.
2. An organosolv process for treating a lignocellulosic 11. The process of claim 1 or 2 wherein the biomass com
biomass comprising: prises annual fibre feedstock.
a. Adding the biomass to a reaction vessel and exposing the 12. The process of claim 1 or 2 wherein the yield of lignin
biomass to a solvent wherein: recovered from the extraction liquor is 60% or greater of the
i. the ratio of solvent to biomass is from about 10:1 to theoretical maximum yield.
about 4:1; 13. The process of claim 1 or 2 wherein the yield of lignin
ii. the solvent comprises from 40 to 60% w/w ethanol: recovered from the extraction liquor is 70% or greater of the
iii. the pH of the biomass/solvent mixture is from about theoretical maximum yield.
2.5 to about 2.7; 14. The process of claim 1 or 2 wherein the yield of lignin
b. Elevating the temperature of the biomass/solvent mix recovered from the extraction liquor is 80% or greater of the
ture to from about 150° C. to about 170° C. for a total theoretical maximum yield.
period of from about 50 minutes to about 200 minutes to 15. The process of claim 1 or 2 wherein the pretreated
form a pulp and an extraction liquor said liquor compris biomass solids have a TCT equal to 120h or less and an OGC
ing extracted derivatives of native lignin; of 50% or higher.
c. Recovering the extraction liquor; 16. The process of claim 1 or 2 wherein at least a portion of
d. Recovering the pulp; and the recovered pulp is converted into carbohydrates which are
wherein the pressure in the reaction vessel is about 22 bar Subsequently converted into ethanol.
or less. k k k k k