US 2007.

0034345A1
(19) United States
(12) Patent Application Publication (10) Pub. No.: US 2007/0034345 A1
PETRUS et al. (43) Pub. Date: Feb. 15, 2007
(54) PROCESS FOR ORGANOSOLV PULPING (57) ABSTRACT
AND USE OF A GAMMA LACTONE N A
SOLVENT FOR ORGANOSOLV PULPNG
The invention provides a process for organosolv pulping,
(76) Inventors: Leonardus PETRUS, Amsterdam wherein solid lignocellulosic feed material is heated at a
(NL); Catharina Johanna Maria temperature in the range of from 50 to 210°C. in a solvent
Petrus-Hoogenbosch, legal to obtain a solid cellulosic fraction comprising at least 50 wt
representative, BB Heemskerk (NL) % of the cellulose present in the feed material and a liquid
fraction, wherein the solvent comprises at least 10 wt % of
Correspondence Address: a compound according to general molecular formula
SHELL OIL COMPANY
PO BOX 2463
HOUSTON, TX 772522463 (1)
R6
Rs
(21) Appl. No.: 11/420,981 O
R4
(22) Filed: May 30, 2006
O R3
(30) Foreign Application Priority Data R R2
Jun. 15, 2005 (EP)........................................ O5105245.4
Publication Classification wherein R to Reach represent, independently, a hydrogen
atom or an organic group connected with a carbon atom to
(51) Int. Cl. the lactone group. The invention further provides the use of
D2IC 3/20 (2006.01) a compound according to general molecular formula (1) in
(52) U.S. Cl. ................................................. 162/72; 162/24 a solvent for organosolv pulping.
US 2007/0034345 A1
PROCESS FOR ORGANOSOLV PULPNG AND
USE OF A GAMMA LACTONE IN A SOLVENT
FOR ORGANOSOLV PULPNG
CROSS-REFERENCE TO RELATED
APPLICATION
0001. This application claims priority from European
Patent Application No. 05105245.4, filed Jun. 15, 2005,
which is incorporated herein by reference.
FIELD OF THE INVENTION
0002 The present invention provides a process for orga
nosolv pulping and the use of a gamma lactone in a solvent
for organosolv pulping.
BACKGROUND OF THE INVENTION
0003. The most widely used pulp manufacturing process
is the Kraft process. An important drawback of the Kraft
pulping process is, however, that a large mineral waste
stream comprising harmful components is formed. In order
to avoid the formation of mineral waste material, organosolv
pulping has been proposed and studied as an alternative for
Kraft pulping. In organosolv pulping, lignocellulosic mate
rial is heated in a solvent comprising organic compounds
and optionally water, in order to dissolve the greater part of
the hemicellulose and lignin and to obtain a high-quality,
high-molecular weight cellulose that is Suitable for paper
production. The solvent is separated from the dissolved
hemicellulose and lignin by simple distillation for recycling.
0004 Well-known solvents for organosolv pulping com
prise organic compounds such as lower aliphatic alcohols,
for example methanol or ethanol, lower carboxylic acids, for
example formic acid or acetic acid, acetone, polyhydric
alcohols, for example ethylene glycol or glycerol, or mix
tures thereof. Often water is part of the solvent, typically in
an amount up to 50 wt %. A small amount of strong mineral
acid, typically in the range of a few tenths to a few percent,
may be added as catalyst to the solvent. Oxidants such as
hydrogen peroxide or peroxy acids may be added to the
Solvent to improve bleaching.
0005 Organosolv pulping is typically carried out at a
temperature in the range of from 80 to 180°C. The operating
pressure mainly depends on the volatility of the solvent. The
pressure should be such that the solvent is still in the liquid
phase. Typically, organolsolv pulping is performed just
below the boiling temperature of the liquor. A drawback of
the use of relatively volatile solvents is therefore that
relatively high operating pressures are needed.
0006 An extensive overview of prior art organosolv
processes is given in E. Muurinen, “Organosolv Pulping A
review and distillation study related to peroxyacid pulping.
University of Oulu, Finland, 2000, ISBN 951-42-5661-1.
SUMMARY OF THE INVENTION
0007. It has now been found that compounds having a
gammalactone group can very Suitably be used as solvent or
part of the solvent for organosolv pulping.
0008 Accordingly, the present invention provides a pro
cess for organosolv pulping, wherein solid lignocellulosic
feed material is heated at a temperature in the range of from
50 to 210°C. in a solvent to obtain a solid cellulosic fraction
Feb. 15, 2007
comprising at least 50 wt % of the cellulose present in the
feed material and a liquid fraction, wherein the solvent
comprises at least 10 wt % of a compound according to
general molecular formula
(1)
R6
O
Rs
R4
O R3
R R2
wherein R to Reach represent, independently, a hydrogen
atom or an organic group connected with a carbon atom to
the lactone group.
0009. In a further aspect, the invention provides the use
of a compound according to general molecular formula (1)
in a solvent for organosolv pulping.
0010. An important advantage of the use of a compound
having a gamma lactone group in a solvent for organosolv
pulping is that it has a relatively high boiling point and that
the organosolv pulping can thus be carried out at a relatively
low pressure.
0011. A further advantage of the process and the use
according to the invention is that the compound according to
general molecular formula (1) is both polar and relatively
inert. As a consequence, it is an effective organosolv solvent
that does hardly form reaction products with the lignocel
lulosic feed material or with components formed during the
organosolv process.
DETAILED DESCRIPTION OF THE
INVENTION
0012. The process according to the invention is a process
for organosolv pulping wherein a Solid lignocellulosic feed
material is heated in a solvent comprising at least 10 wt %
of a compound having a gamma lactone group to obtain a
solid cellulosic fraction and a liquid fraction. The liquid
fraction contains the solvent and dissolved hemicellulose
and lignin degradation products. The aim of organosolv
pulping is to obtain a high-quality solid cellulose fraction or
cellulose pulp that is suitable for paper production. There
fore, the exact process conditions in terms of temperature,
pressure, heating time and the solvent used are chosen Such
that the greater part of the cellulose remains intact, i.e. is not
depolymerised and dissolved in the liquid fraction. In the
process according to the invention at least 50 wt % of the
cellulose present in the feed material is recovered in the solid
cellulosic fraction, preferably at least 60 wt %, more pref
erably at least 80 wt %. The cellulose content of the feed
material and of the solid cellulose fraction obtained may for
example be determined by hydrolysing a sample of the
material followed by identification and quantification of
Sugars by means of gas chromatography according to TAPPI
method T 249 cm-00. After correction of the glucose value
by Subtracting the glucose portion derived from the gluco
mannan present in the sample, the cellulose content is
calculated from the corrected glucose value.
0013 Preferably, the solid cellulosic fraction obtained
has an average degree of polymerisation of at least 300.
US 2007/0034345 A1
Reference herein to the average degree of polymerisation of
the cellulose is to the weight-average degree of polymeri
sation. The degree of polymerisation may be determined by
measuring the Viscosity of a solution of the cellulosic
fraction of known concentration, for example according to
TAPPI method T 230 Om-04.
0014) Preferably, at least 50 wt % of the lignin in the
lignocellulosic feed material is removed from the feed
material during the organosolv process according to the
invention, more preferably at least 80 wt %.
0.015 The lignocellulosic feed material is heated in the
Solvent at a temperature that is typical for organosolv
processes, i.e. in the range of from 50 to 210°C., preferably
of from 100 to 200° C., more preferably of from 80 to 180°
C.
0016. The solvent used in the process according to the
invention comprises at least 10 wt % of a compound having
a gamma lactone group, i.e. a compound according to
general molecular formula (1). Preferably, the solvent com
prises at least 20 wt % of such compound, more preferably
at least 50 wt %, even more preferably at least 80 wt %,
based on the total weight of the solvent.
0017 Reference herein to the solvent is to the total liquid
phase in which the solid feed material is heated. Apart from
one or more compounds according to general molecular
formula (1), the solvent may comprise further organic com
pounds that are known solvents for organosolv pulping.
Examples of Such known compounds are lower aliphatic
alcohols such as methanol or ethanol, polyhydric alcohols,
in particular diols with the hydroxyl groups on adjacent
carbon atoms such as ethylene glycol, glycerol. 1,2-pro
panediol or 2,3-butanediol, lower carboxylic acids such as
formic acid or acetic acid, and acetone. The solvent may also
comprise water, preferably in an amount up to 50 wt %,
more preferably up to 20 wt %.
0018. The solvent may comprise an acid catalyst. Any
acid known to be Suitable as catalyst in organosolv pulping
may be used. In particular strong mineral acids such as
phosphoric acid, Sulphuric acid, hydrochloric acid and nitric
acid, are known to be very effective catalysts for organosolv
pulping. The catalyst preferably is a strong mineral or
organic acid with a pKa below 2.5. Preferred strong mineral
acids are phosphoric acid and Sulphuric acid, more prefer
ably phosphoric acid. Preferred strong organic acids are
oxalic acid, 2-oxopropanoic acid, maleic acid, and 2.4.6-
trihydroxibenzoic acid. Combinations of acids may also be
used.
0019. It is preferred to keep the concentration of mineral
compounds in the solvent as low as possible in order to
avoid mineral waste streams. The acid catalyst, in particular
in case of a mineral catalyst, is therefore preferably present
in a concentration of below 5 wt % of the solvent, more
preferably in a concentration in the range of from 0.01 to 3.0
wt %, even more preferably of from 0.05 to 1.0 wt %. For
a heating temperature in the range of from 100 to 210°C.,
it is preferred to use a solvent that is free of mineral acid.
Feb. 15, 2007
Therefore, in a preferred embodiment of the process accord
ing to the invention, the feed material is heated at a tem
perature in the range of from 100 to 210°C., more preferably
of from 120 to 180° C., in a solvent that is free of mineral
acid. For lower heating temperatures, i.e. below 100° C., the
presence of an acid catalyst in the solvent is preferred.
0020. The lignocellulosic feed material may be any ligno
cellulosic material known to be a suitable feedstock for
pulping processes. Examples of Such materials are hard
wood, Softwood, bagasse, wheat Straw, miscanthus, Switch
grass, reed, or flax. The feed material may be in any form
known to be Suitable for organosolv pulping, typically in the
form of particles with dimensions in the order of a few
centimetres, for example wood chips or cutted Stalks.
0021. The organosolv process according to the invention
may be carried out in a batch, semi-batch or continuous
operation. In a batch operation, the ratio of Solvent to Solid
feed material is preferably in the range of from 2 to 50, more
preferably of from 3 to 15. In a continuous operation, i.e.
with continuous Supply and discharge of solvent, the liquid
hourly velocity of the solvent is preferably in the range of
from 1 to 50 litre solvent per kg feed material per hour, more
preferably of from 2 to 25 litre/kg/h.
0022 Reference herein to a compound having a gamma
lactone group is to a compound according to general
molecular formula (1), wherein R to R each represent,
independently, a Hatom or an organic group connected with
a carbon atom to the lactone group. The total number of
carbon atoms of the compound is preferably at most 20,
more preferably at most 15.
0023 The compound according to general molecular
formula (1) preferably is a compound wherein R. R. R.
and R are a hydrogen atom, more preferably a compound
wherein R. R. R. and R are a hydrogen atom and Rs is a
methyl group. Examples of Such more preferred compounds
are gamma Valerolactone (R is a hydrogen atom) also
known as 5-methyldihydrofuran-2(3H)-one, 2-methyl-5-ox
otetrahydrofuran-2-carboxylic acid (R is a carboxyl group),
a compound having a molecular structure according to any
one of molecular formulas (2) to (5):
(2)
H3C O
O
OH
O O
(3)
O
H3C
HC
O OH
O
O
US 2007/0034345 A1
-continued
(4)
O
O
HC
O
O ester of an acid according to molecular formula (2), (3), (6)
O
(5)
O at most 5 carbon atoms, even more preferably a methyl or an
H3C
CH3
O tion, the feed material is preferably heated in the solvent at
O preferably of from 1 to 5 bar (absolute). Since compounds
or an ester of a compound having a molecular structure
according to molecular formula (2) or (3).
0024. The compounds according to formulas (2) to (5)
are levulinic acid dimers that may be obtained by contacting
levulinic acid in the presence of hydrogen with a strongly
acidic catalyst having a hydrogenating function, e.g. Pd/cat
ion-exchange resin, at elevated temperature and preferably
at elevated pressure. Typical process temperatures and pres
sures are in the range of from 60 to 170° C. and of from 1
to 200 bar (absolute), respectively. Such process for
levulinic acid dimerisation is described in detail in co
pending patent application EP 04106107.8. The catalyst and
process conditions of this process are similar to those
applied in the known single-step process for the production
of methyl isobutyl ketone from acetone.
0025. Other compounds with a gamma lactone group
suitable to be used in the solvent of the organosolv process
according to the invention, which are obtainable by the
above-mentioned levulinic acid dimerisation process, are the
compounds with a molecular structure according to formula
(6) or (7) or their esters:
(6)
HO
CH, O into compounds that boil at a lower temperature than the
Feb. 15, 2007
-continued
(7)
O
O
O
HO
CH
CH3
0026 If the compound with a gamma lactone group is an
or (7), then the ester preferably is an alkyl ester with an
alcohol fragment with at most 10 carbon atoms, more
preferably a linear alkyl ester with an alcohol fragment with
ethyl ester.
0027. In the organosolv process according to the inven
a pressure in the range of from 1 to 10 bar (absolute), more
according to general formula (1) have a relatively low
Volatility as compared to conventional organosolv Solvents
like lower aliphatic carboxylic acids or alcohols, the orga
nosolv process according to the invention can be carried out
at relatively low pressures.
0028 Preferably, the compound(s) according to general
molecular formula (1) that are used in the solvent are
recovered for recycling. This may for example be done by
applying the following process steps, after the heating of the
feed material in the solvent as hereinabove described:
0029 (a) separating the solid cellulose fraction from the
liquid fraction;
0030) (b) adding water to the separated liquid fraction
and heating the separated liquid fraction in the presence of
an acid catalyst at a temperature in the range of from 100
to 300° C. to obtain a hydrolysed liquid fraction;
0031 (c) distilling lower boiling compounds in the
hydrolysed liquid fraction from the compound according
to general molecular formula (1); and
0032 (d) using the compound according to general
molecular formula (1) obtained in step (d) in the solvent
wherein the feed material is heated.
0033. In step (a), the solid and liquid fraction obtained in
the organosolv process according to the invention are sepa
rated from each other by conventional means, e.g. filtration.
The thus-obtained liquid fraction comprises solvent and
dissolved feed material degradation products, mainly depo
lymerised hemicellulose and lignin. In step (b), the liquid
fraction is further hydrolysed after addition of water in order
to convert the dissolved feed material degradation products
compound according to general molecular formula (1).
Hydrolysis step (b) is carried out in the presence of an acid
catalyst. In case the liquid fraction already contained an acid
catalyst, i.e. the acid catalyst used in the organosolv step, no
US 2007/0034345 A1 Feb. 15, 2007

additional catalyst needs to be added. In case the organosolv means of gas chromatography according to TAPPI method T
step has been carried out without an acid catalyst, an 249 cm-00.
homogeneous or heterogeneous acid catalyst, preferably a
heterogeneous acid catalyst, has to be added to the liquid TABLE
fraction obtained in step (a). EXAMPLES 1 to S
0034. In step (c), the hydrolysed dissolved feed material
degradation products are distilled from the compound(s) T residue
cellulose
content
according to general molecular formula (1). If lower boiling EXAMPLE Solvent (C.) (wt %) residue
conventional solvent compounds were present in the Sol
vent, for example methanol, ethanol, formic acid or acetic 1 10.0 wt % gVL* 1OO 47 n.d.**
90.0 wt % formic acid
acid, they will also be distilled from the compound(s) 2 90 wt % gVL 150 43 n.d.**
according to general molecular formula (1). If, however, 10 wt % oxalic acid
high boiling conventional compounds for organosolv Sol 3 97.1 wt % gVL 175 34 8O
vents are present in the solvent, i.e. compounds with a 2.5 wt % phosphoric acid
0.4 wt % water
comparable or higher boiling point than the compound 4 89.2 wt % gVL 175 65 63
according to formula (1), they will be retained in the bottom 10.8 wt % formic acid
fraction, together with the compound according to general 5 78.6 wt % gVL 175 57 72
molecular formula (1). 20.7 wt % ethylene glycol
0.6 wt % phosphoric acid
0035) In step (d), the compound according to general 0.1 wt % water
molecular formula (1) is recycled to the organosolv step to gVL: gamma Valerolactone
be used in the solvent. **n.d.: not determined
0036. It is an advantage of the process according to the
invention that the solvent boils at a relatively high tempera
ture and, thus, the solvent may be recycled by distilling the What is claimed is:
hydrolysed dissolved feedstock degradation products from 1. A process for organosolv pulping, wherein Solid ligno
the solvent. In conventional organosolv processes, the Sol cellulosic feed material is heated at a temperature in the
vent boils at a lower temperature and, thus, the solvent needs range of from 50 to 210°C. in a solvent to obtain a solid
to be distilled from the feed degradation products, which cellulosic fraction comprising at least 50 wt % of the
requires a larger distillation capacity. cellulose present in the feed material and a liquid fraction,
wherein the solvent comprises at least 10 wt % of a
EXAMPLES compound according to general molecular formula
0037. The process according to the invention will be
further illustrated by means of the following non-limiting (1)
examples. R6
Rs
O
Examples 1 to 5 R4
0038 Approximately 4 grams of dried birchwood (Betula O R3
ssp.) sawdust having a cellulose content of 49 wt % was
weighted into the reactor tube of a plug flow reactor. Solvent R R2
was continuously supplied to and discharged from the reac
tortube at a liquid hourly velocity of 8 litre per kg wood per wherein R to Reach represent, independently, a hydrogen
hour. The reactor pressure was kept at 4 bar (absolute). atom or an organic group connected with a carbon atom to
During the first hour, the solvent was heated from room the lactone group.
temperature to the reaction temperature, then the tempera 2. A process according to claim 1, wherein the Solid
ture was maintained for one hour at the reaction temperature cellulosic fraction comprises at least 60 wt % of the cellulose
and then the solvent was cooled from reaction temperature present in the feed material.
to room temperature. After cooling, the solvent Supply was 3. A process according to claim 1, wherein the cellulose
stopped and acetone was supplied to the reactor to remove in the Solid cellulosic fraction obtained has an average
remaining liquid from the Solid residue. The acetone-washed degree of polymerisation of at least 300.
residue was dried by purging it overnight with nitrogen, 4. A process according to claim 1, wherein the feed
removed from the reactor, and weighed. material is heated at a temperature in the range of from 100
0039. During all experiments, a dark liquid fraction was to 200° C.
discharged from the reactor tube and the acetone-washed 5. A process according to claim 1, wherein the solvent
residue obtained, i.e. the solid cellulosic fraction, had a comprises at least 20 wt % of the compound according to
considerably lighter colour than the feed material. general molecular formula (1).
0040. In the Table, the composition of the solvent, the 6. A process according to claim 1, wherein the solvent
reaction temperature, the amount of residue as percentage of comprises an acid catalyst.
the weight of the feed material and the cellulose content of 7. A process according to claim 6, wherein the acid
the residue are shown for EXAMPLES 1 to 5. The cellulose catalyst is a strong mineral acid having a pKa below 2.5.
content was determined by hydrolysing all polysaccharides 8. A process according to claim 6, wherein the acid
followed by identification and quantification of Sugars by catalyst is a strong organic acid having a pKa below 2.5.
US 2007/0034345 A1 Feb. 15, 2007

9. A process according to claim 6, wherein the acid

catalyst is present in a concentration of at most 5% by -continued
weight of the solvent. (5)
O
10. A process according to claim 1, wherein the feed
material is heated at a temperature in the range of from 100 O
to 210°C. in a solvent that is free of mineral acid.
HC
11. A process according to claim 1, wherein the feed
material is heated in the solvent at a pressure in the range of O
CH3
from 1 to 10 bar (absolute).
12. A process according to claim 1, wherein R. R. R.
and R each are a hydrogen atom. O

13. A process according to claim 12, wherein Rs is a

methyl group.
14. A process according to claim 13, wherein the com
pound according to general molecular formula (1) is gamma
Valerolactone (R is a hydrogen atom), 2-methyl-5-oxotet
rahydrofuran-2-carboxylic acid (R is a carboxyl group), a
compound having a molecular structure according to any
one of molecular formulas (2) to (5):
or an ester of a compound having a molecular structure
according to molecular formula (2) or (3).
15. A process according to claim 1, wherein the com
pound having a gamma lactone group has a molecular
structure according to molecular formula (6) or (7):
(6)
O

HO
(2)
O
H3C CH, O
O
O (7)
O
OH
O O O
O
(3)
O
HO
H3C
CH
H3C CH

O OH
or is an ester of a compound having a molecular structure
O according to molecular formula (6) or (7).
16. Use of a compound according to general molecular
O formula (1) in a solvent for organosolv pulping.
(4)
17. A process according to claim 1, wherein the solid
O cellulosic fraction comprises at least 80 wt % of the cellulose
present in the feed material.
O 18. A process according to claim 2, wherein the cellulose
in the Solid cellulosic fraction obtained has an average
degree of polymerisation of at least 300.
H3C 19. A process according to claim 2, wherein the feed
material is heated at a temperature in the range of from 100
O to 200° C.
20. A process according to claim 3, wherein the feed
material is heated at a temperature in the range of from 100
to 200° C.