CA2136733A1 - Process for activation of cellulose - Google Patents
Process for activation of celluloseInfo
- Publication number
- CA2136733A1 CA2136733A1 CA002136733A CA2136733A CA2136733A1 CA 2136733 A1 CA2136733 A1 CA 2136733A1 CA 002136733 A CA002136733 A CA 002136733A CA 2136733 A CA2136733 A CA 2136733A CA 2136733 A1 CA2136733 A1 CA 2136733A1
- Authority
- CA
- Canada
- Prior art keywords
- range
- cellulose
- streams
- weight percent
- activation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/02—Rendering cellulose suitable for esterification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
2136733 9325584 PCTABScor01 Disclosed is a process comprising: A) introducing cellulose and water into an activation zone; B) introducing acetic acid and sulfuric acid into the activation zone; and C) subjecting the cellulose, water, acetic acid and a catalyst to an agitation in the range of 0.04 to 4.0 kilowatts per pound of the combined weight of the cellulose, water, acetic acid and sulfuric acid for a period of time of less than 10 seconds.
Description
~ w~g3,25~84 21~ 3 P~T/~93/~516~
.
; .
... . '.
PROCESS FOR ACTIVATION OF CELLULOSE , ~;
This invention relates to a process for activation `
of cellulose~wherein the cellulose is sub~ected to high j . .
agitation for a short periad of time~
T ~ .u~a~ ` e 54 CellUl^5Q a~QtZtQ b~in~ina with wood pulp, the wood pulp is ~ypically supplied to l~ ;
the manufacturer in ~he form of a re}atively dense sheet ~ ~ 2~ ~h` ~ n c_=~___ ~__ ~_ ~ a ~____ _SSQd into bales. The wood pulp does not readily disinteyrate to form a composition capable or under yoing acetylation '~
and therefore the sheets of wood pulp must be prepared ~.
.for the acetyl~ition step in a prior step typically ~.
rererred to as 'tactivation". l~.
In accordanc2 with methods well known in the art, .
the ac.i~Jatio~ step can ~2 ~ u_~2d:~y ~.ech~nic_lly sub~dividing tAe sheet of wood pulp a~d then conkact~ng ~1.
: the units of sub-divided wood pulp with acetic materials ~r a: ~2r;~: Q~ ti~e. .j;~
; Although the activa~ion proces~es of t~e pri~r art l:
are effective~in producing a composition which can be l.:
satisfactorily acetylated, these processes require .
~25 relatively long pe~iods of time. For:example, the ~:~
activation processes of the prior art typically require times of several hours and or~en require times or more ~:th~ 2 hours. Due to the time ~alue of:capital, it wou}d be very desirable to reduce the time required to '''.','!':' conduc~ the activation process. ..
We have now discovered a process for the acti~ation : of cellulose which can be conduc~ed in an extremely ~, : ch¢rt ~eriod o time comDared to the procqsses of the : prior art.~ We have accomplished the objective of conducting the activation process in a very short time ~.
by subjecting the activation composition to a very high rate of agitation.
, ~
, .
W~93/25~84 ,~ r PCT/US93/051~
~la6qB~ i '' . ~
.
; .
... . '.
PROCESS FOR ACTIVATION OF CELLULOSE , ~;
This invention relates to a process for activation `
of cellulose~wherein the cellulose is sub~ected to high j . .
agitation for a short periad of time~
T ~ .u~a~ ` e 54 CellUl^5Q a~QtZtQ b~in~ina with wood pulp, the wood pulp is ~ypically supplied to l~ ;
the manufacturer in ~he form of a re}atively dense sheet ~ ~ 2~ ~h` ~ n c_=~___ ~__ ~_ ~ a ~____ _SSQd into bales. The wood pulp does not readily disinteyrate to form a composition capable or under yoing acetylation '~
and therefore the sheets of wood pulp must be prepared ~.
.for the acetyl~ition step in a prior step typically ~.
rererred to as 'tactivation". l~.
In accordanc2 with methods well known in the art, .
the ac.i~Jatio~ step can ~2 ~ u_~2d:~y ~.ech~nic_lly sub~dividing tAe sheet of wood pulp a~d then conkact~ng ~1.
: the units of sub-divided wood pulp with acetic materials ~r a: ~2r;~: Q~ ti~e. .j;~
; Although the activa~ion proces~es of t~e pri~r art l:
are effective~in producing a composition which can be l.:
satisfactorily acetylated, these processes require .
~25 relatively long pe~iods of time. For:example, the ~:~
activation processes of the prior art typically require times of several hours and or~en require times or more ~:th~ 2 hours. Due to the time ~alue of:capital, it wou}d be very desirable to reduce the time required to '''.','!':' conduc~ the activation process. ..
We have now discovered a process for the acti~ation : of cellulose which can be conduc~ed in an extremely ~, : ch¢rt ~eriod o time comDared to the procqsses of the : prior art.~ We have accomplished the objective of conducting the activation process in a very short time ~.
by subjecting the activation composition to a very high rate of agitation.
, ~
, .
W~93/25~84 ,~ r PCT/US93/051~
~la6qB~ i '' . ~
- 2 - ~
1~
In summary, our invention can be thought of as ';
: ~ a process comprising ':
~ (A) introducing cellulose and water into an i~:.
; activation zone, ' "::: 5 ~B) introducing acetic acld and a catalyst into i, the activatiQn æo~
: (C) subjecting the cellulose, wa~er, acetic acid , . . .
: and catalyst to an agitation in the range of ~ ~ - ~3 4~ OW~-I ~ 2~ ~5'~-~ ~r~
combined weight o~ the first and second streams for a period of time of less than 10 : seconds. .~Theiwood pulp, o~ten call~d cellulose, which is ;:
: useful in our process can comprise any or ;the wood pulps typically sold in the trade. :Speci$ic examples of ,~:
suitable cellulose:include so~thern and Canadian 1.
hardwoods and so~twoods.
The units of cellulose sheet must have a cross sectional diameter of le5s th~t 2 ~h~ hi5 ~ h~
' '.: ' 1 "
20~ ~accomplished by me~hznically sub-dividing the sneet of cellulose into:units of this size by meth~ds well known ; in tne ar~, such~as a hammer mill.
The amount of ce}lulose which is:introduced into ~:~
:: the~activation zone is broadly~in the range of 1 to 60 ;25~ w ~ er~en~, prereraDly in the range:o~ 30 to 55 weight percent, based on the co~bined weight o~ t_e ''"~' : ::celluloser water, acetic acid and catalyst. ;.
: The céllulose can be introduced into the activationzone by donventional means such as allowing the 30 : cellulose units to fall under the in~luen~e of gravity from the means to su~-di~ide the units into activation 20ne. Pre~erably, the cellulose is~sub-:~ ~ : divided in a hammer mill and the unit~:of:sub-divided~ .
cellulose are allowed to ~all from the exit of the f ..:.
! ' 1~''.'.
: ' ~' G~
W093/25;84 2 ~ PCT/US93/05164 ,~ $ '~' Y~
:' .' - 3 ~ :
.. ..
hammer mill into the en~ry port of the apparatus used to ..
perform the high agitation.
The amount of water in the which is introduced into the activation zone is broadly in the range of 0 to g9 weight pexcent, preferable in the range of 2 to 20 cellulose, water, acetic acid and catalyst.
The water is introduced into the activation zone .~.
U,inC C;~ Je.. l,i::~ai ~ n ~ e~a 1J 3PinY ::~?2- U... ~e- j pressure.
The ~irst step of the process of this invention has been described as in~roducing a first stream of both ,.
cellulose and water into the activation zone. While the pr~ferred emDodiment is for both the cellulose and wa~er i.
~o be c~ined ~nto one st_ez~ it is fully w~th~n the i,.
scope o- t~.e:invention far the ceilulose and wa~er ~o be introduced into the actiuation zone as ~eparate streams. ;:
The acetic acid use~ul in the ~econd step of the ~ce~ ~f t h~s nuen~i~n is the tv~e t~icallv used in ~ .
the prepaxation oî celiulose acetate and is well known in the art. Preferably glacial acetic acid is used. I'~
;~ : The catalyst useful in the second step of the process of this invention can be methane ~ulfonic acid, methane disulfonic acid, sulfoac2tic acid, sulfuryl chloride or sulfuric acid. P~eferably the catalyst is _~f"-'~ ac~ a~d ~s~e Fr~ y LS ~% s~ u~ic acid.
The acetic acid and cataIyst are introduced into the activation zone using conventional means, preferably being pumped under pressure.
: . 30 The serond step of the process o~ this invention . .
dQscxibed æs ~ntroducin a second stream of : both acetic acid and catalyst into the acti~ation zone.
While the p~eferred embodiment is for the acetic acid . and catalyst to be com~ined into one stream it is fully within the scope of the invention for these materials to ' .
':
W093t~5584 .,~ ` PCT/US93/051~4.
2136~33 .. ..
1~
In summary, our invention can be thought of as ';
: ~ a process comprising ':
~ (A) introducing cellulose and water into an i~:.
; activation zone, ' "::: 5 ~B) introducing acetic acld and a catalyst into i, the activatiQn æo~
: (C) subjecting the cellulose, wa~er, acetic acid , . . .
: and catalyst to an agitation in the range of ~ ~ - ~3 4~ OW~-I ~ 2~ ~5'~-~ ~r~
combined weight o~ the first and second streams for a period of time of less than 10 : seconds. .~Theiwood pulp, o~ten call~d cellulose, which is ;:
: useful in our process can comprise any or ;the wood pulps typically sold in the trade. :Speci$ic examples of ,~:
suitable cellulose:include so~thern and Canadian 1.
hardwoods and so~twoods.
The units of cellulose sheet must have a cross sectional diameter of le5s th~t 2 ~h~ hi5 ~ h~
' '.: ' 1 "
20~ ~accomplished by me~hznically sub-dividing the sneet of cellulose into:units of this size by meth~ds well known ; in tne ar~, such~as a hammer mill.
The amount of ce}lulose which is:introduced into ~:~
:: the~activation zone is broadly~in the range of 1 to 60 ;25~ w ~ er~en~, prereraDly in the range:o~ 30 to 55 weight percent, based on the co~bined weight o~ t_e ''"~' : ::celluloser water, acetic acid and catalyst. ;.
: The céllulose can be introduced into the activationzone by donventional means such as allowing the 30 : cellulose units to fall under the in~luen~e of gravity from the means to su~-di~ide the units into activation 20ne. Pre~erably, the cellulose is~sub-:~ ~ : divided in a hammer mill and the unit~:of:sub-divided~ .
cellulose are allowed to ~all from the exit of the f ..:.
! ' 1~''.'.
: ' ~' G~
W093/25;84 2 ~ PCT/US93/05164 ,~ $ '~' Y~
:' .' - 3 ~ :
.. ..
hammer mill into the en~ry port of the apparatus used to ..
perform the high agitation.
The amount of water in the which is introduced into the activation zone is broadly in the range of 0 to g9 weight pexcent, preferable in the range of 2 to 20 cellulose, water, acetic acid and catalyst.
The water is introduced into the activation zone .~.
U,inC C;~ Je.. l,i::~ai ~ n ~ e~a 1J 3PinY ::~?2- U... ~e- j pressure.
The ~irst step of the process of this invention has been described as in~roducing a first stream of both ,.
cellulose and water into the activation zone. While the pr~ferred emDodiment is for both the cellulose and wa~er i.
~o be c~ined ~nto one st_ez~ it is fully w~th~n the i,.
scope o- t~.e:invention far the ceilulose and wa~er ~o be introduced into the actiuation zone as ~eparate streams. ;:
The acetic acid use~ul in the ~econd step of the ~ce~ ~f t h~s nuen~i~n is the tv~e t~icallv used in ~ .
the prepaxation oî celiulose acetate and is well known in the art. Preferably glacial acetic acid is used. I'~
;~ : The catalyst useful in the second step of the process of this invention can be methane ~ulfonic acid, methane disulfonic acid, sulfoac2tic acid, sulfuryl chloride or sulfuric acid. P~eferably the catalyst is _~f"-'~ ac~ a~d ~s~e Fr~ y LS ~% s~ u~ic acid.
The acetic acid and cataIyst are introduced into the activation zone using conventional means, preferably being pumped under pressure.
: . 30 The serond step of the process o~ this invention . .
dQscxibed æs ~ntroducin a second stream of : both acetic acid and catalyst into the acti~ation zone.
While the p~eferred embodiment is for the acetic acid . and catalyst to be com~ined into one stream it is fully within the scope of the invention for these materials to ' .
':
W093t~5584 .,~ ` PCT/US93/051~4.
2136~33 .. ..
- 4 - .:
' .''.' be introduced into the activa~ion zone as separate streams. ~;
The amount of acetic acid is broadly in the range 1.
of 1 ko 99 weight percent, preferably in the range sf 30 i.
to 50 weiyht percent, based on the combined weight of th_ c~ lc,c, -~at r, a~z~ic ~cld and ca~alyst~
The amount of catalyst is broadly in the range of . .....
0.2 to 6 weight.percent, preferably in the ra~ge of 1 to~:
3 -~ei~ pe_cen-, ~zsea n t:~_ c^~inl-d ~e~ c~
cellulose, water, acetic acid and catalyst.
Th~ process of this in~ention can be operated : ei~her as a batch process or a continuous process. ::
Preferably, the process in operated as a continuous : process. ;:' This inv~ntion has been described in terms or ~irst ..
introducing the~stream of cellulose ~nd water into the ;i;
activation zone and then introducing the stream of acetic acid and catalyst Lnto the activaticn ~on_.
r~ k~~, t~.~ r-~~~S~ e~a~ ~m~sly ~nd ,~
bo~h~oî ~hese streams are introduced into the activation : zone simultaneousl~ he proc~s is pr2r iced cn 2 batch basis, the streams can be introduced in any ord~r : or can be introduced simultaneously.
Agitation of the activation composition is a critical ~eature o~ this invention. In thls invention, ~' ~G ~ icn co3pcsi~ion i5 as~tated within a particular range. The range is expressed in ~2rms of the requirement;for elestrical energy to mechanically . perform ~he agitation and is broadly in the range of ~:~
~:: 3Q 0.04 to 4.0 kilowatts per pound, preferably 0.1 tG 1 ' cw~s pe- po~n~, of thr cs.~k~nPd weight oE
: cellulose, water, acetic acid and catalyst.
Mechanical pparatus required to achieve this rate of agi~ation is well known in the art and is commercially ava~lable. Since a mixing function is .. ..
';'.
W~93/25~84 ~l 3 ~ 7 3 3 P~ 9~
' .
' .''.' be introduced into the activa~ion zone as separate streams. ~;
The amount of acetic acid is broadly in the range 1.
of 1 ko 99 weight percent, preferably in the range sf 30 i.
to 50 weiyht percent, based on the combined weight of th_ c~ lc,c, -~at r, a~z~ic ~cld and ca~alyst~
The amount of catalyst is broadly in the range of . .....
0.2 to 6 weight.percent, preferably in the ra~ge of 1 to~:
3 -~ei~ pe_cen-, ~zsea n t:~_ c^~inl-d ~e~ c~
cellulose, water, acetic acid and catalyst.
Th~ process of this in~ention can be operated : ei~her as a batch process or a continuous process. ::
Preferably, the process in operated as a continuous : process. ;:' This inv~ntion has been described in terms or ~irst ..
introducing the~stream of cellulose ~nd water into the ;i;
activation zone and then introducing the stream of acetic acid and catalyst Lnto the activaticn ~on_.
r~ k~~, t~.~ r-~~~S~ e~a~ ~m~sly ~nd ,~
bo~h~oî ~hese streams are introduced into the activation : zone simultaneousl~ he proc~s is pr2r iced cn 2 batch basis, the streams can be introduced in any ord~r : or can be introduced simultaneously.
Agitation of the activation composition is a critical ~eature o~ this invention. In thls invention, ~' ~G ~ icn co3pcsi~ion i5 as~tated within a particular range. The range is expressed in ~2rms of the requirement;for elestrical energy to mechanically . perform ~he agitation and is broadly in the range of ~:~
~:: 3Q 0.04 to 4.0 kilowatts per pound, preferably 0.1 tG 1 ' cw~s pe- po~n~, of thr cs.~k~nPd weight oE
: cellulose, water, acetic acid and catalyst.
Mechanical pparatus required to achieve this rate of agi~ation is well known in the art and is commercially ava~lable. Since a mixing function is .. ..
';'.
W~93/25~84 ~l 3 ~ 7 3 3 P~ 9~
' .
- 5 - , ~
.
inevitably associated with the high rate of agitation, ' this apparatus is often re~erred to as a "mixer". :~
Specifically, the apparatus is often called a high ~:
consistency mixer by those ~killed in the art.
Pre~erably the apparatus is a Model 48 Micar High Con5is ~ency mixer sola Dy Black Clawson, Snar~le Di~ision. Other apparatus suitable for use in this invention are d~sclosed in U.S. 4,016,353. !.
~ 2 F~e-e--e~ c~ ~G,,~ hg~e ~h_ appara~us is a Model 48 Micar High Consistency mixer the first stream is introduced into the hopper of the apparatus and tne .;
second s~ream is introduced into the highly agitated :~
mixiny barrel. ~.
The per~oa of time the acti~ation composition is subjected to the high rate or agilation is an extremely :-.
impor~ant ~ea~ure o~ ~his inven~ion. The period of time .
the activation mixture is subjected to the high rate of :
agitat~en ls ~roadl~ less ~kan ~0 seconds, pr~4e~b~ y The ac.ivation composition is subjected to the high rats o~ ~gita~n ~c- ~e sp_~ifi c pe-iod ~ ti~e ~y operating the mixer continuously and adjusting the rotor~stato- con~iguration.
~ The process of this invention has been described as an "acti~ation proeess". By the term "activation ~:
p,oc ~s~'-we m2~n ~hat the compos-tion wnich exits rrom the mixer can, in ~ome instances, be fully activated and therefore can be immediately introduced into the acetylation step without the necessity to age the : 30 composition for a period of time. By this term we also mean ~hu ~ th- composl~o~ -~hlch ~xlts from the mixer is not fully activated and must be aged prior to :introduction of the composition into the acetylation step. Whether any additional aging is required, or how much additional aging is required, varies widely WO93/255g4 ,~,~ . . PCT/US93/0516~
213~733 ~:
,.. . ~
,. `:
depending on numerous factors understood by those skilled in the art, such as the temperature ~f the .;
c~mposition, the type of catalyst and the amount of catalyst. Typically, the composition i5 aged for a ,.
period of time in the range of 10 minutes to 3 hours,.`.:~
preferably 20 min~tes to ~o m~' n~ ¢, As has been discussed earlier, an advantage of this invention is that the time ~or the activation s-tep is .
5ig~if l 52n~ s~ a- ~ . -h~_~, 2-~-n when aging is required the combination of the time . requir~d for agitation and the time required for aging -.
: : .is ~ill slgni~icantly less t~an the time for the ~`.
a~tivation steps of the prior art. ::.
The practice of this in~ention can be iilustra~ed by the fo~lowing example.
A hammer mill is posit~cned s~ch that the outpu~ o.
sub-divided cellulose units will fall into the hopper or a Model 48 Micar ~igh Consistency mixer sold by Black Clawson, Shartle Di~sion~ The highlv agitated mix~.g : 20 barrel entry port o_ the ~ixer is adapted with piping to : receive th~ a s~ream of acetic acid and sulfuric acid.::
: A con~inuouC activation process is then conducted~.
wh~rein a roll of hardwood cellulose containin~ water is ~.
fed into the hammer mill at ambient conditions and sub-: 25 dl~id~d i~o units:having a cross sectional diameter of:~
: less than 2 inches which fall i~to the ho~er of the continuously operating mixer. The composition of this ~;
stream is 96 lbs~min cellulos~ and 4 lbs~min water. 84 i lbs~min acetic acid and 4 lbs~min sulfuric acid are continuously pumped into the mixer through the highly :: agitated mixing barrel entry port. The rate o~ ;
~: agitation is adjusted to 1.5 to 2.5 kilowatts per pound of the combined weight of all four components. Based on the physical configuration o~ the mixer, the time the :~
' ~ ..
.:.
,.
~:
.W093/2~84 ~ 13 6 7 3 3 PCT/US93/05~64 ,' , . ...
, .. .
- 7 - ,.
, ... .
activation composition is subjected to this rate of ~-agitation for 1 to 3 seconds.
The composition exiting from the mixer was aged 20 to ~0 minutes to become ~ully activated and fed to a conventional acetylation process and successfully ,~.
~ ace~ylated in~o a product which was further processed by ,.
: ~ conventional means inko commercially acceptable ; cellulose aceta~e. :.
.:"
.
, .
. '`;
. ~ . . .
~ ~ ; : . , , :
:-: ~ ~ : ,' ~ :
`::
'.;
:
, ,
.
inevitably associated with the high rate of agitation, ' this apparatus is often re~erred to as a "mixer". :~
Specifically, the apparatus is often called a high ~:
consistency mixer by those ~killed in the art.
Pre~erably the apparatus is a Model 48 Micar High Con5is ~ency mixer sola Dy Black Clawson, Snar~le Di~ision. Other apparatus suitable for use in this invention are d~sclosed in U.S. 4,016,353. !.
~ 2 F~e-e--e~ c~ ~G,,~ hg~e ~h_ appara~us is a Model 48 Micar High Consistency mixer the first stream is introduced into the hopper of the apparatus and tne .;
second s~ream is introduced into the highly agitated :~
mixiny barrel. ~.
The per~oa of time the acti~ation composition is subjected to the high rate or agilation is an extremely :-.
impor~ant ~ea~ure o~ ~his inven~ion. The period of time .
the activation mixture is subjected to the high rate of :
agitat~en ls ~roadl~ less ~kan ~0 seconds, pr~4e~b~ y The ac.ivation composition is subjected to the high rats o~ ~gita~n ~c- ~e sp_~ifi c pe-iod ~ ti~e ~y operating the mixer continuously and adjusting the rotor~stato- con~iguration.
~ The process of this invention has been described as an "acti~ation proeess". By the term "activation ~:
p,oc ~s~'-we m2~n ~hat the compos-tion wnich exits rrom the mixer can, in ~ome instances, be fully activated and therefore can be immediately introduced into the acetylation step without the necessity to age the : 30 composition for a period of time. By this term we also mean ~hu ~ th- composl~o~ -~hlch ~xlts from the mixer is not fully activated and must be aged prior to :introduction of the composition into the acetylation step. Whether any additional aging is required, or how much additional aging is required, varies widely WO93/255g4 ,~,~ . . PCT/US93/0516~
213~733 ~:
,.. . ~
,. `:
depending on numerous factors understood by those skilled in the art, such as the temperature ~f the .;
c~mposition, the type of catalyst and the amount of catalyst. Typically, the composition i5 aged for a ,.
period of time in the range of 10 minutes to 3 hours,.`.:~
preferably 20 min~tes to ~o m~' n~ ¢, As has been discussed earlier, an advantage of this invention is that the time ~or the activation s-tep is .
5ig~if l 52n~ s~ a- ~ . -h~_~, 2-~-n when aging is required the combination of the time . requir~d for agitation and the time required for aging -.
: : .is ~ill slgni~icantly less t~an the time for the ~`.
a~tivation steps of the prior art. ::.
The practice of this in~ention can be iilustra~ed by the fo~lowing example.
A hammer mill is posit~cned s~ch that the outpu~ o.
sub-divided cellulose units will fall into the hopper or a Model 48 Micar ~igh Consistency mixer sold by Black Clawson, Shartle Di~sion~ The highlv agitated mix~.g : 20 barrel entry port o_ the ~ixer is adapted with piping to : receive th~ a s~ream of acetic acid and sulfuric acid.::
: A con~inuouC activation process is then conducted~.
wh~rein a roll of hardwood cellulose containin~ water is ~.
fed into the hammer mill at ambient conditions and sub-: 25 dl~id~d i~o units:having a cross sectional diameter of:~
: less than 2 inches which fall i~to the ho~er of the continuously operating mixer. The composition of this ~;
stream is 96 lbs~min cellulos~ and 4 lbs~min water. 84 i lbs~min acetic acid and 4 lbs~min sulfuric acid are continuously pumped into the mixer through the highly :: agitated mixing barrel entry port. The rate o~ ;
~: agitation is adjusted to 1.5 to 2.5 kilowatts per pound of the combined weight of all four components. Based on the physical configuration o~ the mixer, the time the :~
' ~ ..
.:.
,.
~:
.W093/2~84 ~ 13 6 7 3 3 PCT/US93/05~64 ,' , . ...
, .. .
- 7 - ,.
, ... .
activation composition is subjected to this rate of ~-agitation for 1 to 3 seconds.
The composition exiting from the mixer was aged 20 to ~0 minutes to become ~ully activated and fed to a conventional acetylation process and successfully ,~.
~ ace~ylated in~o a product which was further processed by ,.
: ~ conventional means inko commercially acceptable ; cellulose aceta~e. :.
.:"
.
, .
. '`;
. ~ . . .
~ ~ ; : . , , :
:-: ~ ~ : ,' ~ :
`::
'.;
:
, ,
Claims (2)
Claims
1. A process comprising (A) introducing into an activation zone a first stream comprising cellulose which has a cross sectional diameter of less than 2 inches and is in the range of 1 to 60 weight percent and water in the range of 0 to 99 weight percent, based on the combined weight of the first and second streams, (B) introducing into the activation zone a second stream comprising acetic acid in the range of 1 to 99 weight percent and a catalyst selected from the group consisting of methane sulfonic acid, methane disulfonic acid, sulfoacetic acid, sulfuryl chloride and sulfuric acid in the range of 0.2 to 6 weight percent, based on the combined weight of the first and second streams, and (C) subjecting the first and second streams to an agitation in the range of 0.04 to 4.0 kilowatts per pound of the combined weight of the first and second streams for a period or time of less than 10 seconds.
2. A process comprising (A) introducing into an activation zone a first stream comprising cellulose which has a cross sectional diameter of less than 2 inches and is in the range of 30 to 55 weight percent and water in the range of 2 to 20 weight percent, based on the combined weight of the first and second streams, (B) introducing into the activation zone a second stream comprising acetic acid in the range of 30 to 50 weight percent and sulfuric acid in the range of 1 to 3 weight percent, based on the combined weight of the first and second streams, and (C) subjecting the first and second streams to an agitation in the range of 0.1 to 1 kilowatts per pound of the combined weight of the first and second streams for a period of time of less than 5 seconds.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US89711392A | 1992-06-11 | 1992-06-11 | |
| US07/897,113 | 1992-06-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2136733A1 true CA2136733A1 (en) | 1993-12-23 |
Family
ID=25407353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002136733A Abandoned CA2136733A1 (en) | 1992-06-11 | 1993-06-01 | Process for activation of cellulose |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0644901A1 (en) |
| JP (1) | JPH08501326A (en) |
| KR (1) | KR950701649A (en) |
| BR (1) | BR9306539A (en) |
| CA (1) | CA2136733A1 (en) |
| WO (1) | WO1993025584A2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5973139A (en) * | 1998-02-06 | 1999-10-26 | Eastman Chemical Company | Carboxylated cellulose esters |
| US20080071078A1 (en) * | 2006-09-19 | 2008-03-20 | Kizer Lawton E | Method of making cellulose ester polymer and pre-treating cellulose for the manufacture of cellulose ester polymer |
| DE102008035401B4 (en) * | 2008-07-29 | 2011-04-21 | List Holding Ag | Process for the continuous catalytic acetylation of polysaccharides |
| EA024244B1 (en) * | 2013-04-09 | 2016-08-31 | Сумгаитский Государственный Университет | Process for producing cellulose powder |
| EA024275B1 (en) * | 2013-04-09 | 2016-09-30 | Сумгаитский Государственный Университет | Process for producing activated cellulose |
| EA024220B1 (en) * | 2013-04-30 | 2016-08-31 | Сумгаитский Государственный Университет | Process for producing activated cellulose powder |
| EA024257B1 (en) * | 2013-05-24 | 2016-08-31 | Сумгаитский Государственный Университет | Process for cellulose activation |
| EA024276B1 (en) * | 2013-06-19 | 2016-09-30 | Сумгаитский Государственный Университет | Process for cellulose activation |
| WO2016009461A1 (en) | 2014-07-14 | 2016-01-21 | 株式会社ダイセル | Method for disintegrating pulp for cellulose acetate production, and process for producing cellulose acetate |
| RU2609803C1 (en) * | 2015-09-28 | 2017-02-06 | Общество с ограниченной ответственностью "Твин Технолоджи Компани" | Ways to enhance quality and reactivity of cellulose |
| WO2023137154A1 (en) | 2022-01-14 | 2023-07-20 | Greenkey Llc | Process for treating land-based plant and marine-based biomasses |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4016353A (en) * | 1975-04-14 | 1977-04-05 | Crown Zellerbach Corporation | Process for producing organic acid esters of cellulose |
| JP2999293B2 (en) * | 1991-07-02 | 2000-01-17 | ダイセル化学工業株式会社 | Method for producing cellulose acetate |
-
1993
- 1993-06-01 BR BR9306539A patent/BR9306539A/en not_active Application Discontinuation
- 1993-06-01 KR KR1019940704224A patent/KR950701649A/en not_active Application Discontinuation
- 1993-06-01 WO PCT/US1993/005164 patent/WO1993025584A2/en not_active Application Discontinuation
- 1993-06-01 EP EP93921169A patent/EP0644901A1/en not_active Withdrawn
- 1993-06-01 CA CA002136733A patent/CA2136733A1/en not_active Abandoned
- 1993-06-01 JP JP6501538A patent/JPH08501326A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO1993025584A3 (en) | 1994-02-17 |
| JPH08501326A (en) | 1996-02-13 |
| BR9306539A (en) | 1998-09-15 |
| EP0644901A1 (en) | 1995-03-29 |
| KR950701649A (en) | 1995-04-28 |
| WO1993025584A2 (en) | 1993-12-23 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| FZDE | Dead |