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US008394999B2

(12) Ulllted States Patent (10) Patent N0.: US 8,394,999 B2


Ding et al. (45) Date of Patent: Mar. 12, 2013

(54) PROCESS FOR CONVERTING GLYCERIN (51) Int. Cl.


INTO PROPYLENE GLYCOL C070 29/132 (2006-01)
(52) US. Cl. ..................................................... .. 568/861
(75) Inventors: Zh0ngyi Ding, Katy, TX (Us); JOSQPh (58) Field of Classi?cation Search ................. .. 568/861
Chill, Katy, TX (Us); Weihlla Jill, Katy, See application ?le for complete search history.
TX (US)
(56) References Cited
(73) Assignee: GTC Technology US LLC, Houston,
TX (U S) US. PATENT DOCUMENTS
_ _ _ _ _ 7,586,016 B2 * 9/2009 Cui et a1. .................... .. 568/861
( * ) Not1ce: Subject to any disclaimer, the term ofthis 7,619,113 B2 * 11/2009 Anedondo et a1 ,,,,,,,, u 564/471
patent is extended or adjusted under 35 * _ _
U.S.C. 154(1)) by 0 days. ted by examlner
p10Z Primary Examiner i ElVlS 0 Price
(74) Attorney, Agent, or Firm * Winstead PC
(22) Filed: Mar. 12, 2012
(57) ABSTRACT
(65) Prior Publication Data A process to convert glycerin into propylene glycol and puri
US 2012/0232312 A1 Sell 13, 2012 fying the produced propylene glycol is described. The glyc
erin-based propylene glycol production requires only one
process step compared to petroleum/natural gas-based pro
Related US Application Data pylene glycol production requires multiple process steps, and
thus represents a cost savings.
(60) Provisional application No. 61/451,246, ?led on Mar.
10, 2011. 11 Claims, 1 Drawing Sheet
US. Patent Mar. 12, 2013 US 8,394,999 B2

599mm Maximise

Mam-m
US 8,394,999 B2
1 2
PROCESS FOR CONVERTING GLYCERIN sel production enables the production of glycerin in large
INTO PROPYLENE GLYCOL quantities at very loW costs, Which quali?es it for future
development as one of the building block chemicals.
CROSS-REFERENCES TO RELATED Propylene glycol is the preferred choice due to its estab
APPLICATIONS lished market and large consumption. One particularly inter
esting propylene glycol substitution is its use as a green
This Application claims the bene?t under 35 USC 119(e) non-toxic antifreeZe and de-icing ?uid. Propylene glycol is
of US. Provisional Patent Application Ser. No. 61/451,246 currently produced from petrochemical derived propylene. It
?led Mar. 10, 201 1, Which is incorporated herein by reference has broad established market applications and potential for
in its entirety as if fully set forth herein. other applications. The successful conversion of glycerin to
propylene glycol and the utiliZation of glycerin as a potential
FIELD OF THE INVENTION petrochemical feedstock shall positively impact the biodiesel
business through better carbon utiliZation, by-product
This invention relates to a process for converting glycerin upgrade to high value products, opportunity to develop
to propylene glycol and purifying the propylene glycol that is 5 reneWable chemicals, and maximum return on investment.
produced.
SUMMARY OF THE INVENTION
BACKGROUND OF THE INVENTION
An aspect of the invention is directed to a process for
The World is collectively engaged in a massive search for 20 converting glycerin into propylene glycol comprising the
energy alternatives to ever higher priced crude oil. Among steps of: preheating a feed mixture comprising glycerin,
these alternatives, biodiesel has gained importance in recent hydrogen and methanol in a reactant heater; passing the
years for its ability to mix With petroleum diesel. Biodiesel heated feed mixture to a reactor; separating the reactor e?iu
refers to a diesel-equivalent fuel consisting of short chain ent into a vapor phase stream and a liquid phase stream;
alkyl (methyl or ethyl) esters, made by transesteri?cation of 25 condensing the vapor phase stream into a condensed liquid;
triglycerides, commonly knoWn as vegetable oils or animal recycling the condensed liquid to the reactor; and distilling
fats. The most common form uses methanol, the cheapest the liquid phase stream to obtain puri?ed propylene glycol.
alcohol available, to produce methyl esters. The molecules in The cost advantage for this glycerin based propylene gly
biodiesel are primarily fatty acid methyl ester (FAME), usu col process over petroleum-based propylene glycol produc
ally created by transesteri?cation betWeen fats and methanol. 30 tion stems from its simplicity. The glycerin-based propylene
Currently, biodiesel is produced from various vegetable and glycol production requires only one process step Whereas
plant oils. petroleum/natural gas-based propylene glycol production
One by-product of the transesteri?cation process is glyc requires multiple process steps.
erin (glycerol). For every 1 ton of biodiesel manufactured,
100 kg of glycerin is produced. Historically, there Was a 35 BRIEF DESCRIPTION OF THE DRAWINGS
valuable market for the glycerin, Which assisted the econom
ics of the overall biodiesel process. With the increase in global FIG. 1 shoWs a process scheme for the conversion of glyc
biodiesel production, hoWever, the by-product glycerin has erin into propylene glycol in accordance With an embodiment
saturated the market, Which in turn has caused the market of the invention.
price of the crude glycerin to fall. The valuable disposition of 40
this crude glycerin is vitally important to making the reneW DESCRIPTION OF EXEMPLARY
able biodiesel process more e?icient in carbon utiliZation EMBODIMENTS
While offsetting production costs.
Glycerin usage is primarily used in foods and beverages, A hydrogenation process is used to convert glycerin into
pharmaceutical and personal care, and ?ne chemicals. Glyc 45 propylene glycol (PG). The process has greater than 95%
erin is an oxygenated three carbon chemical. With the rapid selectivity to PG and produces 98% or higher purity PG for
expansion of biodiesel production, glycerin has become an industrial applications. An exemplary process scheme is
abundant and inexpensive raW material. This character brings shoWn in FIG. 1.
glycerin in as a potential chemical building block for other An embodiment of the invention is directed to a process for
important reneWable/ green chemicals. 50 converting glycerin into propylene glycol comprising the
TWo main classes of petrochemical raW materials are ole steps of: preheating a feed mixture comprising glycerin,
?ns (including ethylene and propylene) and aromatics (in hydrogen and methanol in a reactant heater; passing the
cluding benZene and xylene isomers), both of Which are pro heated feed mixture to a reactor; separating the reactor e?iu
duced in very large quantities. They are the building blocks of ent into a vapor phase stream and a liquid phase stream;
chemicals and plastics We are using daily. These petroleum 55 condensing the vapor phase stream into a condensed liquid;
based commodity chemicals are not immune to resource limi recycling the condensed liquid to the reactor; and distilling
tation and increasing cost that We face in the fuel industry the liquid phase stream to obtain puri?ed propylene glycol.
today. The search of alternative sources is vital important. The The claimed invention is directed to a process for convert
strategic development for technologies in bio-chemicals and ing glycerin to propylene glycol. The process scheme com
process integration With biofuels could be similar to the cur 60 prises a reaction section to convert glycerin to propylene
rent petroleum-based processes. The building block chemi glycol and a fractionation section to obtain on-spec propylene
cals must be relatively easy and cheap to produce in large glycol product. A proprietary catalyst is used comprising a
quantities. They should have chemical structures that facili metal or metal oxide dispersed on inert support. The hydro
tate their conversion into multiple products of commercial genation reaction of glycerin is carried out at a temperature of
interest. Therefore, both bioethanol and glycerin have poten 65 approximately 1900 C. and a pressure of 2.0-8.0 MPa (20-80
tial to be the building block chemicals for petroleum-based atmospheres). One-pass glycerin conversion is greater than
ethylene and propylene derivatives. The moderniZed biodie 70% and propylene glycol selectivity is greater than 95%. The
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propylene glycol is further puri?ed in the fractionation sec In an embodiment of the invention, the vapor phase stream
tion to meet various product speci?cations. is separated from the liquid phase stream using a high pres
An embodiment of the invention is directed to a process for sure gas-liquid separator. In other embodiments of the inven
the conversion of glycerin to propylene glycol by hydroge tion, the vapor phase stream is separated from the liquid phase
nation in a ?xed bed reactor at a temperature of 150 C.-240o stream using a column With liquid Wash.
C. and a pressure of 20-80 atmospheres. In certain embodi In an embodiment of the invention, the vapor phase stream
ments of the invention, the reaction temperature is approxi contains recycle solvent such as Water, methanol, or other loW
mately 1900 C. In other embodiments of the invention, the boiling point chemicals. In another embodiment of the inven
operating pressure of the reactor is 20-60 atmospheres. tion, the recycle solvent is a mixture of Water and methanol. In
In some embodiments of the invention, the hydrogenation a further embodiment of the invention, the recycle solvent is
of glycerin to propylene glycol is performed by a supported mixed With a glycerin feed and passed into the ?xed bed
catalyst in a ?xed bed reactor. In certain embodiments the reactor.
supported catalyst is a metal or metal oxide catalyst. In some In an embodiment of the invention, a portion of the recycle
embodiments the metal or metal oxide catalyst comprises a solvent and glycerin mixture is injected betWeen tWo ?xed
noble metal, transition metal, or a combination of transition bed reactors connected in a series.
metals. In certain embodiments of the invention, the sup In an embodiment of the invention, the liquid phase stream
ported catalyst comprises copper. is depressuriZed and then cooled before entering a distillation
As set forth in FIG. 1, in an embodiment of the inventive column. In other embodiments of the invention, the liquid
process, a glycerin feed, along With hydrogen and methanol, phase stream is ?rst cooled and then depressuriZed before
is preheated in a feed-ef?uent heat exchanger and reactant 20 entering a distillation column.
heater. The mixture then enters the reactor Where the hydro In certain embodiments of the invention, multiple distilla
genation of glycerin to PG takes place. The reactor ef?uent, tion columns are used in the puri?cation of propylene glycol.
passes through a feed-ef?uent heat exchanger, and enters a These distillation columns can be selected from single shell
high pressure separator, Where hydrogen and methanol are column, column With side draW, or divided-Wall column.
separated from PG and glycerin liquid stream. The vapor 25 In certain embodiments of the invention, a ?rst distillation
phase is cooled and the condensed solvent andboosted hydro column is used in certain embodiments to separate fuel gas
gen are recycled to the reactor. and methanol from the reactor e?luent. The ef?uent from the
In an embodiment of the invention, the liquid stream from ?rst distillation column is passed into a second distillation
the high pressure separator is cooled doWn and de-pressuriZed column. The second distillation column is used to separate
before entering distillation section. In other embodiments of 30 alcohols, Water and acetol mixture from the reactor ef?uent.
the invention, the liquid stream is depressuriZed and then The ef?uent from the second distillation column is passed to
cooled doWn. In an embodiment of the invention, the reactor a third distillation column. The third distillation column is
e?luent is passed through three distillation columns, column used to separate PG, PG/ethylene glycol (EG) mixture and
1, column 2 and column 3, to separate the reactor e?luent into recycle glycerin from the reactor e?luent.
the folloWing streams: fuel gas, methanol, mixed alcohols, 35 In an embodiment of the invention, the by-products of the
process Water, acetol mixture (for recycle or product), 99.5% process are separated by distillation. In certain embodiments,
PG, PG/EG mixture, and recycle glycerin. A ?rst distillation by-products are mixed alcohols, Water, ethylene glycol,
column is used in certain embodiments to separate fuel gas acetol, and other trace compounds. In certain embodiments of
and methanol from the reactor e?luent. The e?luent from the the invention, the by-product ethylene glycol is a mixture of
?rst distillation column is passed into a second distillation 40 propylene glycol and ethylene glycol, or high purity ethylene
column. The second distillation column is used to separate glycol. In other embodiments of the invention, the by-product
alcohols, Water and acetol mixture from the reactor e?luent. mixed alcohols contain Water. In certain embodiments of the
The e?luent from the second distillation column is passed to invention, by-products methanol, Water, acetol, and ethylene
a third distillation column. The third distillation column is glycol are obtained from side-draW at different distillation
used to separate PG, PG/ethylene glycol (EG) mixture and 45 columns.
recycle glycerin from the reactor e?luent. The claimed invention possesses several advantages over
In an embodiment of the invention, a hydrogenation pro prior art processes including:
cess for converting glycerin into propylene glycol comprises 1 . LoWer capital co st production compared to conventional
a ?xed bed reactor loaded With a supported metal or metal PG from Propylene oxide (PO) route;
oxide catalyst, Where the majority of glycerin in the feed is 50 2. Energy integration options to further reduce operating
converted into propylene glycol. The reactor e?luent passes costs;
into a feed-ef?uent heat exchanger, and the vapor phase 3. One-step reaction from glycerin to PG With higher selec
stream is separated from the liquid phase stream. The vapor tivity;
phase is further condensed and the condensed liquid is 4. Attractive, competitive technology;
recycled to the ?xed bed reactor. The liquid phase is further 55 5. Technology platform in reneWable resources; other tech
separated by distillation to obtain puri?ed propylene glycol. nologies could be built along the claimed process;
In an embodiment of the invention, the ?xed bed reactor 6. Integrated With biodiesel process for best utiliZation of
can be one ?xed reactor, tWo ?xed reactors in series, or carbon resources; and
multi-?xed bed reactors in series. 7. Green chemical as feedstock glycerin is from bio-reneW
In another embodiment of the invention, the ?xed bed 60 able source.
reactor is operated at temperature of 1500 C.-240o C., and Although the present invention has been described in con
pressure of 20-60 atmospheres. nection With some embodiments, it is not intended to be
In other embodiments of the invention the supported metal limited to the speci?c form set forth herein. Rather, the scope
or metal oxide catalyst that is used in the inventive process is of the present invention is limited only by the accompanying
selected from noble metal, transition metal, or a combination 65 claims. Additionally, although a feature may appear to be
of transition metals. In other embodiments of the invention, described in connection With particular embodiments, one
the supported catalyst comprises copper. skilled in the art Would recogniZe that various features of the
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described embodiments may be combined in accordance With separating the reactor e?luent into a vapor phase stream
the invention. In the claims, the term comprising does not and a liquid phase stream;
exclude the presence of other elements or steps. condensing the vapor phase stream into a condensed liquid;
Furthermore, although individually listed, a plurality of recycling the condensed liquid to the reactor; and
means, elements or method steps may be implemented by eg distilling the liquid phase stream to obtain puri?ed propy
a single unit or processor. Additionally, although individual lene glycol.
features may be included in different claims, these may pos 2. The process according to claim 1, Wherein the reactor is
sibly be advantageously combined, and the inclusion in dif a ?xed bed reactor.
ferent claims does not imply that a combination of features is 3. The process according to claim 1, Wherein the reactor is
not feasible and/or advantageous. Also, the inclusion of a operated at a temperature of 150 C.-240o C.
feature in one category of claims does not imply a limitation 4. The process according to claim 1, Wherein the reactor is
to this category but rather indicates that the feature is equally operated at a pressure of 20-80 atmospheres.
applicable to other claim categories as appropriate. Further 5. The process according to claim 1, further comprising
more, the order of features in the claims do not imply any hydrogenating the heated feed mixture in the reactor.
speci?c order in Which the features must be Worked and in 6. The process according to claim 5, Wherein the hydroge
particular the order of individual steps in a method claim does nating is carried out by a supported catalyst in the ?xed bed
not imply that the steps must be performed in this order. reactor.
Rather, the steps may be performed in any suitable order. In 7. The process according to claim 6, Wherein the supported
addition, singular references do not exclude a plurality. Thus catalyst is a metal or metal oxide catalyst.
references to a, an, ?rst, second etc do not preclude 20 8. The process according to claim 7, Wherein the supported
a plurality. catalyst comprises copper.
9. The process according to claim 1, further comprising
mixing the condensed liquid With a glycerin feed.
The invention claimed is:
10. The process according to claim 1, Wherein the liquid
1. A process for converting glycerin into propylene glycol phase stream is depressuriZed and cooled prior to distilling.
comprising the steps of: 25
11. The process according to claim 1, Wherein the liquid
preheating a feed mixture comprising glycerin, hydrogen phase stream is distilled in multiple distillation columns.
and methanol in a reactant heater;
passing the heated feed mixture to a reactor; * * * * *