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METHYL ISOBUTYL CARBINOL MIXTURE
AND METHODS OF USING SAME
Inveator: Bo L. Tran, Chicago IL (US)
Assignee: Naleo Company, Naperville, IL (US)
Notice: Subject to any disclaimer, the term ofthis
pateat is extended or adjusted under 35
USC. 154(b) by O days
This patent is subject to a terminal dis-
claim,
Appl. Now 137053825
Filed: Sun. 19,2012
Prior Publication Data
US 201201117721 May 10,2012
Related US. Application Data
Continuation-in-part of application No, 11/764.461
filed on Jun. 18, 2007, now Pat. No 8,123,082.
Int. Cl
BOSE 1/04 (2006.01)
B0sD 1/008 (2006.01)
BOSD IM (2006.01),
us.cl, 209/166: 252/61
Field of Classification Search 200/166:
252/61
See pplication file for complete search history.
'US008302778B2
(10) Patent No.
4s) Date of Patent:
US 8,302,778 B2
*Nov. 6, 2012
66) References Cited
US. PATENT DOCUMENTS
137088 A +1991 Sayre 200166
yoo A+ S935 Paek doves
DS00A2T § * 111942. Christman eal 200 166
Soran A T1913 Chemeb eta
ROSSI A 41976. Schmit eal
A207 AGIOS) Manger
#500284 8 $2198) reson ea aos?
S316s64 A $1994 Gropol eal
So2s06 A 7/199) Rast etal
Sioxow Ree 22012 Tram 2091166
* cited by examiner
Primary Examiner — ‘Thomas M Lithgow
(74) Attornes, Agent, or Firm —Benjamin E_ Carlsen:
Andrew D. Sorenson
on ABSTRACT
Te invention is directed towards methods and compositions
for sepamting materials are provided. The present invention
provides a method of separating first material from a second
Iaterial such as mixing the frst material and the second
‘material in a slunry with a beneliciation composition, The
‘benefciation composition can comprise meth isobutyl
carbinol mixture derived fom & methy! isobutyl Ketone and
‘methyl isobutyl carina! manufacturing process. Adition-
ally air bubbles can be provided in the slurry to form bubble
particle aggregates with the first material and the bubble-
particle agarepates can be allowed to be separated from the
evondl material
15€
1s, No DrawUS 8,302,778 B2
1
METHYL ISOBUTYL CARBINOL MIXTURE
AND METHODS OF USING SAME,
(CROSS-REPERENCE TO RELATED
"APPLICATIONS,
‘his Application is @ continuation in pat of US. patent
application Ser. No, 11/764,461 now US, Pat, No, 8,123,042,
filed on Jun, 18, 2007
STATEMENT REGARDING FEDERALLY
SPONSORED RESEARCH OR DEVELOPMENT
‘Not Applicable.
BACKGROUND OF THE INVENTION
‘The present invention relates generally to beneficiation
technologies, More specifically, the present invention relates
to heneficiation compositions and methods of using the same
Benefication isa method of separating usefal matter fom
waste. Commonly, beneficiation uses the difference in the
hydrophobicity of the respective components. During this
process, the mineral oes comminuted toa certsin smal size
‘and sluried with water. The slurry is introduced into a lo
tion apparatus purged with az The ae bubbles formed prel-
‘erential attach (0 the hydrophobic particles ofthe slurry,
‘making them float tthe top of the apparatus. The floated
particles are collected, dewatered, and accumlated as sell
able final product, Thehydrophilc particles tend to migrateto
the bottom of the contact vessel from where they ean be
removed as slings and processed into waste impoundments
Inother processes, such as everse Hotton, the sellable final
product may migrate tothe bottom.
“To facilitate benetciation, several types of conventional
reagents are used such as frothers, collectors, promoters and
‘conditioners. Nevertheless, these reagents can be expensive
thereby reducing the costeTectiveness ofthe benelieition
processes.
“Thus it is clear that there is clear uiity in novel methods
and compositions forthe flitting beneficiation, The art
described in this section is not intended to constitute aa
admission that any patent, publication or other information
referred to hereia i “Prior Ar” with respect to this invention,
unless specifically designated as such, In addition, this sce
tion should not be construed to meaa that a search has bee
‘made or that ao other pertinent information as defined it 37
CER §1.56(a) exists
BRIEF SUMMARY OF THE INVENTION
At least one embodiment of the invention is directed
‘owanls method of separating a fist material from a second
material. The method comprises: Mining the first material
‘and the second material ina slurry witha eneficiation com-
Position, wherein the boneficiation composition comprises.an
MIBC mixture and at lest one C10 to C18 Ketone, Ain
bubbles may be proved inthe shay to form bubble-particle
‘agarepates withthe fist material; ad allowing the bubble
Particle aggregates tobe separated from the second meri
"AL Teast one embodiment of the invention is directed
towards method of separating a first material from a second
material, the method comprising: Mixing the fist material
and the second material ina slurry with a benefiiation com-
Position derived from the manufacture of methyl isobutyl
ketone of methyl isobutyl earinol, wherein the henefiinton
‘composition comprises one or more components selected
2
rom a group consisting of disobutyl carbinol and diisobutyl
carbinol isomers ancl combinations thereof, and wherein the
Dbenefciation composition comprises one or more ketone
ranging from C10 to C18.
DETAILED DESCRIPTION OP THE INVENTION
‘The following definitions are provided to determine hav
terms used in this application, and in particular how the
claims, ae to be construed. The onganizaton of the defini-
‘ions is for coavenience only’ and is not intended to Fit any
of the definitions to any particular category.
"Beneficition” means separating. useful matter fom
\aste particularly hydrophobic substances from hydrophi
substances, Suitable processes for accomplishing. this
le, but are not limited to, flotation, reverse flotation and
ilar technologies.
"MIRC mixture” means co-products generated from
MIBK andlor MIBC manufacturing processes.
‘By-Products means by-products derived from biodiese
manufacturing processes, andor transesterification reactions
involving triglycerides
“OFT-Spce Material” cans products rom odie man
facturing processes andiortransesterification reactions that
do not meet industry quality standards because they are bot-
‘oms of processes, contaminated, by-products, and/or gener-
ated from process wash out. The oflspee material can com-
prise the same components as the by-products. In some
‘nstanees, the offspee material is mixed with the by-prod-
vets,
“Cineen Collector” means one of more components
selected from a group consisting of nonionic surfetants of
low HILB numbers, naturally occurring lpi, modified lp
ids, hydrophobic polymers and combinations thereof.
“Green” means environmentally rien, biodegradable,
andor nontoxic chemistry
Tn the event that the above definitions or @ description
stated elsewhere in this application is incoasistent with a
‘meaning (explicit or implicit which is commonly used, in a
ictionary, or stated ina source incorporated by reference into
this application, the application and the elaim terms in par
scala are understood to be construed accoting othe de
sition or description inthis application, and not according to
the common definition, dictionary definition, or the definition
‘that was incorporated by reference. In light of the above, ia
the event that aterm can only be understood iit is consid
by a dictionary, if the term is defined by the KireOthmer
Eneyelopedia of Chemical Technology, Sih Edition, (2005),
(Published by Wiley, John & Sons, Inc.) this definition shall
centrol hav the term isto he defined in the claims.
Flotation processes are one of the most widely used meth
‘ods of separating the valuable material rom valueless mate-
lal present, For example, in a flotation provess, the fine
particles are dispersed in water or other suitable solution and
‘Small sie bubbles are introdveed to the slurry so that hydro-
‘hobic particles ean be selectively collected onthe surface of
the airbubblesandexitthe sury (eg. hy rising tothe surface)
while hydrophilic particles ae lft behind. The hydrophilic
particle ean also siak to the bottom ofthe shumy to be co
lected as sludge.
"The MIBKC mixture can be used to separate materials, for
‘example in any suitable flotation process. tshould be appre-
ciated that the desired final products can rise tothe surface
‘during flotation andor sink to the bottom, such as in reverse
‘oration processes. For example, during silica flotation pro-
cesses, the desired product can sink tothe bottom ofthe srry
and the waste product ean rise tothe top ofthe slurry
0
oUS 8,302,778 B2
3
The present invention provides 4 method of separating 3
first material rom a second material, In one embodiment the
‘method ean comprise mixing the fst material and thesecond
material in a slimy with a beneficiation composition. The
beneliciation composition can comprise a methyl isobutyl
‘carbinol (MIC) mixture. Air bubbles can be provided inthe
shiny to form bubble-particle aggregates with the fist mate-
rial and the bubble-particle aggregates can be allowed to be
separated from the second material
In one embodiment, the MIBC mixture contains MIBC,
‘alcohols, and Ketones.
Tn another embodiment, the MIRC mixture ean be derived
from the manufacture of methyl isobutyl ketone (MIBK)
‘andlor MIBC, The MIRC mixture is co-produced in the
‘manufacturing process
The MIBC mixture comprises about $0 to about 90 weight
pereent of MIBC, about $ t0 about 25 weight percent of
‘alcohols and about 5 to about 25 weight percent of Ketones
in adlitional embodiments
In an embodiment, the aleobols comprise one oF more
‘components selected from a group consisting of disobutyl
‘earinol and diisobuty!carbinol isomers and combinations
thereat
‘nan emboxliment, the Ketones comprise one of more com=
ponents selected from a group consisting of diisobutyl
ketone, isobutyl ketone isomers and 3,3. timethyleyelo-
hhexanone and combinations thereat
Tn embodiment, the MIBC mixture ean be blend with
‘existing beneficiation compositions to improve effectiveness,
Tn another embodiment, the present invention provides 3
‘method of separating hydrophobic and hydrophilic particles
‘nan aqueous stuffy. Por example, the method can comprise
‘adding a beneficiation composition tothe aqueous slurry (0
‘Stabilize the bubble formation The benefciation composition
‘can comprise a MIBC mixture derived from the maalactur
jing of MIBK andlor MIBC. The hydrophobie particles attach
‘ont the surface ofthe stabilized air bubbles, forming bubble=
particle aggregates that can Noat ta the surface ofthe aqueous
slurry.
“The present invention provides an effective methods of
separating to or more materials.
The present invention also provides compositions sed to
Stabilize air bubbles in flotation processes resulting in
improved results
‘The present invention relates generally (0 beneficiation
technologies. More specifically the present invention relates
to heneficiation compositions and methods of using said ben-
eficiaion composition
The present invention provides a benefciation compos!
tions comprising co-praducte from MIBK andlor MIBC
manufacturing processes. The co-productscaneomprise mix-
tures of MIBC and other alcohols and ketones, The aleobols
and ketones contain primarily from nine t0 swenty carbon
"The MIBC mixture ofthe present invention suprisingly
Improves recovery of beneficiation technologies, for
‘example, flotation processes. The MIBC mixture can be wsed
{o supplement or replace conventional beneficiation compo-
sitions used in lotation processes
‘Generally, MIBK is produced Irom acetone. The fist step
involves the aldol condensation to form diacetone aleohol.
‘The diacetone then dehydrated to form mesityoxide. Inthe
last step the mestyl oxide is hydrogenated to MIBK. Theo-
retical yield is about 89%. Varying amounts of MIBC mix-
tures are co-prodiced. MIBC is generally prociced by the
hydrogenation of MIBK.
0
o
4
[MIBK is used primarily asa solventin the coating industry.
(MIRC is used primarily a «lube oil additive. MIBC is also
Widely used a8 a frother in Hotation peocesses recovering
‘minerals. MIBC stabilizes the bubbles allowing the hydeo-
hobic minerals to attach themselves tothe bubbles. low
ever, MIRC cost has esalated recently duc tothe high cst of
petroleum hydrocarbons, The present invention offersan eco-
‘omical alternative that i elfetive fora variety of henficia-
sion technologies,
Tnoneembodiment, the MIBC mixture from MIBK manu
‘cturing can comprise of MIBC, other alcohols and
Ketones, The alcohols and ketones can include diisobuty]
carbinol, diisobuty] Ketone, and 3,3,5 twimethyleyelohex-
‘anone, and their isomers
The above composition suggest that the MIBC mixture
‘can make a perfect flotation reagent. In loation lab tests the
[IBC mixture was eflective in stabilizing air bubbles.
In an altematve embodiment, the MIBC mixtures ean
{urtherbe mixed withadditives to supplement and/or improve
the separation properties ofthe beneficiation compositions.
Such adklitves con include other Rotation reagents. Other
Foation reagents include but are not Himited to ight hydro-
carbon oils, petroleum ethers, fatty acid methyl esters, fatty
‘acids, ¢4-€20 alcohols, o4020 aldehydes, ¢4-c20 esters,
phosphate, sulfate, sulfonate, amine salt, xanhates,hydeo-
phobic polymers, andl combinations thereot
‘he hydrophobic polymers ean inchude, for example, poly
methyihlrosiloxanes,polysilanes, polyethylene derivatives,
‘and hydrocarbon polymers generated by both ring-opening
‘metathesis and methalocene eatalyzed polymerization,
"The light hydrocarbon oils include diesel ol, Kerosene,
gasoline, petroleum distillate, turpentine, naphtanie oils, ete
Tn a further embodinient, the present invention, provides
methods of stabilizing the hubbies in certain beneficiation
processes. For example, the beneficiaton composition com-
prising the MIBC mixture can be usefil in beneliciation of the
following materials including, bat not limited to coal, sand
‘nd gravel, phosphates, diamonds, precious meals, and other
‘mineral ores of manmade matter. In alternative embodi-
‘ments, the benefciation composition can heused in processes
to increase the bubble stability, particulary im applications
such as flotation resulting in the benefciation of eoal, sand
and gravel, phosphates, diamonds, precious metals, and other
‘mineral oes or man-made matte. The beneficiation compo-
lion can also be used in conjunction with tbe suitable
others, flotation collectors and promoters
‘An additonal embodiment of the present invention pro-
vides a method of separating a first material from a second
‘matecal. For example, the method ean comprise mixing the
fist material and the second material ina shay with a ben-
cicition composition, The heneficiation composition can
comprise MIBC mixtures derived Irom a MIBK. or MIBC
‘manufacturing process, Air bubbles caa be provided in the
slumy to form bubble-parcle agzregates with the frst mate-
‘al; the bubble-paticle aggregates can then be separated
from the second material The benefciation composition ean
further include other frothers, promoter, and/or collector
mixed withthe MIBC mixture
The present invention additionally provides a method of
separating hydrophobic and hydrophilic particles in an ague-
ous slury. For example, the method can comprise adding &
bbeneficiation composition to the aqueous shury to inerease
the stability of the bubbles, The benefciation composition
can comprise MIBC mixtures derived from MIBK of MIRC
‘manufacturing process. The aqueous slury can be mixed
‘with the MIRC mixtures. Nie bubbles can be provided to the
aqueous slurry sothat the hydrophobic particles colleet ontheUS 8,302,778 B2
5
surface of hear bubbles forming bubble-particleauprepates.
The bubble-particle agaregates can be allowed to float to the
surface ofthe aqueous sutry tobe separated from the hydro-
Philc particles.
"The materials be separated canhaveanystitablesize. By
‘example and aot limitation, the materials can ange fom 2
‘mm (0 0.04 mm in siz. The slury ean contain up to 50%
solids. Any suitable mechanical or chemical forees can be
used to bring the slury particles in conteet with the benet-
‘ciation compositions of the present invention. The floated
product and the non-osted tailings can becolleted from the
present methods.
‘Some prior art methods and/or compositions relevant 10
bbeneficiation include US. Pat. Nos. 5,316,664, 3,675,773,
‘and 4,208,487. The instant invention differs from these in 3
number of ways. Ina least oneembodiment the henefiiation
method exchides the wse of C9 Ketones, In at least one
‘embodiment the beneficition method excludes the use of
ketones having 9 oF fewer carbon atoms, In at least one
‘embodiment the benefiiation method excludes the presence
(0f2.68 trimethyl-4-nonanone.
EXAMPLES
The foregoing maybe better understood by referenceto the
following examples, whieh are presented for purposes of
‘ustration and are-not intended to limit the seope of the
invention,
Tn example | the beneficition composition ofthe present
Jnvention comprises ablend ofthe MISC mixturesand I-pro-
pene hyoformlation product, The [-propene hyedeofoemy
Tation productisa mixture ofthe C4-C18 alcohols aldehydes
and esters, and is generally used as a frother in tation
‘operations. The beneficiation composition is prepared rom,
about 30% by weight of the MIBC mixtures and 70% by
‘weight of I-propene hydroformylation product. Tt was come
pared against another flotation reagent consisting of 30% hy
‘weight of MIRC and 70% by weight of T-propene hydo-
qomiylation product
“A sample of coal slurry from a coal preparation plant was
Aoated in the laboratory using a Denver flotation machine
‘The tests were designed to determine the ult ofthe MIBC.
mixture blended with a -propene hydroformylation product.
The collector used was diesel. The MIBC mixture was the
‘obtained from the manufacture of MIBK and MIBC.
Example 1
Sytermitce Prepon ne
‘ele 63) we
tae st cv ane
tate at ms Ge
“The above data shows combustible recovery uaproved when,
utilizing the MIBC mixture,
Pxample 2
“The MIBC mixture was used in place of MIBC at eval
Aoation process facility in whieh the recovery of fine coal
noticeably increase from about 85% to 89% withthe we oF
the claimed invention,
0
o
‘While this invention
forms, there described in detail herein specific prelerred
embodiments ofthe invention, The present disclosure is an
cexemplfiation of the principles of the invention and is no,
‘intended o limit the invention tothe particular embodiments
illustrated. All patents, patent application, scientific papers
fand any other referenced materials mentioned herein are
Incorporated by relerence in thee entirety. Purlhermore, the
invention encompasses any possible combination of some or
all of the various embodiments described herein and incor
porated herein. In aldtion the invention encompasses ay
possible combination that also specifically excludes any one
fr some of the various embodiments described heecin and
incorporated herein.
The above disclosure i intended tobe illustrative and not
exhaustive, This description wllsugzest many variations and
altematives to one of ordinary skill in this art All these
fltematives and variations are intended toe incaded within
the scope of the claims where the term “comprising” means
“including, but not Hmited to. Those familiar wilh the at
ay recognize other equivalents othe specific embodiments
described herein which equivalents ae also intended to be
tencompassed by the claims,
‘Allanges and parameters disclosed herein are understood
to encompass any and all subranges subsumed therein, and
every number between the endpoints. For example, a stated
range of" to 10° should be considered to include any and all
subranges between (and inclusive ofthe minimum valve of |
And the maximum value 10; thats all subranges beginning
‘witha minimum, vaueof lormore, eg, 1106.1),andending
‘witha maximum value of 10 oF less, (@.23109.4,3 108.4
07), and finally to each number 1,2,3,4,5,6,7,8,9,and 10
‘contained within the rang.
This completes the description of the prefered and alter-
tate embodiments of the invention, Those skilled inthe at
‘may recognize other equivalents to the specific embodiment
described herein which equivalents are intended to be encom-
passed by the claims ataehed hereto.
‘What is claimed is
1. A method of separating first material from a second
‘material, the method comprising’ mixing the fist material
‘and the second material in a slur with a benefication com-
positon, wherein the beneficiation composition eomprisesan
‘MIRC mixture and the MIRC mixture comprises MIC, at
Teast one C10 to C18 Ketone, 2,6,8rimethy!-4-nonanone,
‘nd one item selected rom the list consisting of 2.6-dim-
ethyl-4heptanol, 2,6