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US008053620B2

c12) United States Patent (IO) Patent No.: US 8,053,620 B2

Sohn et al. (45) Date of Patent: Nov. 8, 2011

(54) GUARD BED FOR REMOVING EP 308962 12/1992

CONTAMINANTS FROM FEEDSTOCK TO A ES 2053664 8/1994
FR 2060354 6/1971
NORMAL PARAFFIN EXTRACTION UNIT GB 1324503 7/1973
GB 1454180 10/1976
(75) Inventors: Stephen W. Sohn, Arlington Heights, IL GB 1510705 5/1978
(US); Mark G. Riley, II, Hinsdale, IL JP 1163139 6/1989
(US) JP 1168629 7/1989
JP 2247135 10/1990
JP 2247137 10/1990
(73) Assignee: UOP LLC, Des Plaines, IL (US) JP 4016450 3/1992
JP 1726445 111993
( *) Notice: Subject to any disclaimer, the term ofthis
(Continued)
patent is extended or adjusted under 35
U.S.C. 154(b) by 398 days.
OTHER PUBLICATIONS
(21) Appl. No.: 12/165,096
Fukunaga, T. et al.; Development of kerosene fuel processing system
(22) Filed: Jun.30,2008 for PEFC; Catalysis Today, 2003, 197-200 (Abstract Only).

(65) Prior Publication Data (Continued)

US 2009/0326305 Al Dec. 31, 2009

Primary Examiner - Tam M Nguyen
(51) Int. Cl. (74) Attorney, Agent, or Firm -Arthur E. Gooding
C07C 7112 (2006.01)
(52) U.S. Cl. .......... 585/820; 208/213; 208/250; 208/57;
585/802; 585/829; 585/831 (57) ABSTRACT
(58) Field of Classification Search ........................ None
See application file for complete search history. Processes and systems for removing contaminants from a
paraffin containing feedstock are provided that include: pro-
(56) References Cited viding a paraffin containing feedstock, passing the paraffin
containing feedstock to an inlet of a guard bed that includes an
U.S. PATENT DOCUMENTS adsorbent material, and contacting the paraffin containing
4,176,053 A * 1111979 Holcombe 208/310 z feedstock with the adsorbent material in the guard bed to
4,963,248 A 10/1990 Yano et al. produce a treated paraffin containing feedstock. The pro-
5,041,693 A 8/1991 Zarchy cesses and systems can also include removing the treated
5,045,178 A 9/1991 Maruyama et al. paraffin containing feedstock from an outlet of the guard bed,
2005/0252831 Al* 1112005 Dysard et al. ................. 208/212
and passing the treated paraffin containing feedstock to a
FOREIGN PATENT DOCUMENTS paraffin separation zone that separates normal paraffins from
BE 755625 3/1971 the treated paraffin containing feedstock.
DE 2043578 3/1971
DE 3876917 2/1993
EP 308962 3/1989 13 Claims, 1 Drawing Sheet

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 US 8,053,620 B2
Page 2

FOREIGN PATENT DOCUMENTS Benashvili, E. M. et al.; Adsorption separation and study of normal
JP 6039432 5/1994 paraffinic hydrocarbons from ligroine-kerosine fractions of
JP 6305988 1111994 Sarngorsk petroleum and a mixture of Sarngorsk, Grozny, and
JP 2520723 7/1996 Shaimsk crudes; Soobshcheniya Akademii Nauk Gruzinskoi SSR,
JP 2520725 7/1996 1979, 369-372 (Abstract Only).
JP 2001294871 10/2001 Mikhal'Skaya, L. I. et al.; Adsorption of sulfur compounds from
JP 3402488 5/2003
kerosene by zeolite; Khimiya i Khimicheskaya Tekhnologiya, 1975,
KR 9604868 4/1996
NL 7012741 3/1971 64-66 (Abstract Only).
OTHER PUBLICATIONS Lobanova, G. A. et al.; Extraction of sulfides from petroleum prod-
ucts by adsorbents; Khimiya i Tekhnologiya Topliv i Massei, 1975,
Sultanov, N. et al.; Activity of adsorbents in the removal of 20-23 (Abstract Only).
heteroorganic compounds from light petroleum products; Khimiya i Mikhal'Skaya, L. I.; Demercaptanization of aviation kerosene on a
Tekhnologiya Topliv i Masal, 1987, 10-11 (Abstract Only). zeolite; Khimiya i Khimicheskaya Tekhnologiya, 1975, 86-90
Al-Khaidar, KH. Y. et al.; Separation of sulfur compounds from (Abstract Only).
kerosine fractions; Azarbaycan Neft Tasarrufati, 1980, 56-59 Makhlitt R. et al.; Adsorption properties of different adsorbents for
(Abstract Only). sulfur compounds of a fraction of jet fuels; Izvestiya Vysshikh
Benashvili, E. M. et al.; Desulfurization of the kerosine fraction of Uchebnykh Zavedenii, Neft i Gaz, 1974, 43-48 (Abstract Only).
petroleum on natural and modified clinoptilolites; 1979 (Abstract
Only). * cited by examiner
U.S. Patent Nov. 8, 2011 US 8,053,620 B2

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 US 8,053,620 B2
1 2
GUARD BED FOR REMOVING affins from the treated paraffin containing feedstock. The
CONTAMINANTS FROM FEEDSTOCK TO A paraffin containing feedstock can be derived from a kerosene
NORMAL PARAFFIN EXTRACTION UNIT boiling range petroleum fraction. The paraffin containing
feedstock can also be hydrotreated prior to being passed to the
TECHNICAL FIELD inlet of the guard bed.
In another aspect, a system for removing contaminants
The processes and systems described herein relate to from a paraffin containing feedstock is provided that includes
removing contaminants from a paraffin containing feedstock. a hydrotreating zone that receives a paraffin containing feed
stock and produces a hydrotreated paraffin containing feed-
DESCRIPTION OF RELATED ART 1o stock, a guard bed, and a paraffin separation zone that receives
the treated paraffin containing feedstock and separates nor-
Products obtained from paraffin containing feedstocks are mal paraffins from the treated paraffin containing feedstock.
useful in a number of applications. In the lighter hydrocarbon The guard bed can have an inlet that receives the paraffin
range, isoparaffins tend to have a high octane value and desir- containing feedstock, a fixed bed where the paraffin contain-
able gasoline alkylation characteristics. In the heavier hydro- 15 ing feedstock contacts an adsorbent material to produce a
carbon range, linear paraffins, also known as normal paraf- treated paraffin containing feedstock, and an outlet from
fins, tend to be desirable for the benefits derived from their which the treated paraffin containing feedstock is removed
linearity in the production of plasticizers, linear alkyl benzene from the guard bed.
sulfonates; detergent alcohols, and ethoxylates. For example,
normal paraffins having carbon numbers in the range ofC 6 to 20 BRIEF DESCRIPTION OF THE DRAWINGS
C 10 can be used for plasticizers, normal paraffins having
carbon numbers in the range C 10 to C 14 can be used for linear Specific examples have been chosen for purposes of illus-
alkylbenzenes, and normal paraffins having carbon numbers tration and description, and are shown in the accompanying
in the range C 10 to C 18 + can be used for detergent alcohols. drawings, forming a part of the specification.
One example of a commercial use for linear paraffins is in 25 FIG. 1 illustrates a simplified schematic diagram of a
the making of detergents. Detergents made from linear alky- hydrotreating zone, a guard bed and a paraffin separation
lbenzene sulfonates (LABs) have become popular because zone.
they have been found to biodegrade more rapidly than deter-
gents made from branched alkylbenzene sulfonates. The pet- DETAILED DESCRIPTION
rochemical industry produces LABs by dehydrogenating nor- 30
ma! paraffins to linear olefins and then alkylating benzene Paraffin containing feedstocks can be any feedstock con-
with the linear olefins in the presence of HF. The normal taining a mixture of normal paraffins and non-normal paraf-
paraffins can be a mixture of linear paraffins having different fins, such as, for example, isoparaffins and/or cycloparaffins.
numbers of carbon atoms per molecule. For example, the Paraffin containing feedstocks preferably comprise C 10 to
normal paraffins can be C 6 to C 22 , or C 10 to C 15 . More narrow 35 C 13 hydrocarbons. For example, paraffin containing feed-
ranges tend to be preferred, such as C 10 to C 12 , or from C 10 to stocks and can comprise C 10 hydrocarbons, C 11 hydrocar-
C13. bons, C 12 hydrocarbons, C 13 hydrocarbons, and mixtures
The recovery of normal paraffins from paraffin containing thereof.
feedstocks can be accomplished in various ways. One process Paraffin containing feedstocks can be derived from hydro-
that has been developed for the production of normal paraffins 40 carbon feedstocks that contain other normal and non-normal
is the Molex process developed by UOP, in Des Plaines, Ill. hydrocarbons, such as olefins, di-isoparaffins, di-isoolefins,
The UOP Molex process is a method for the liquid-phase naphthenes and aromatics. For example, a paraffin containing
adsorptive separation of normal paraffins from isoparaffins feedstock can be derived from a kerosene boiling range petro-
and cycloparaffins. Other processes for the production of leum fraction. A kerosene boiling range petroleum fraction
normal paraffins include vapor-phase processes. 45 can generally be produced by fractionating crude oil. Crude
oil is the liquid part, after being freed from dissolved gas, of
SUMMARY petroleum, a natural organic material composed principally
of hydrocarbons that occur in geological traps. The kerosene
The processes and systems described herein relate to boiling range fraction can contain a mixture of different
removing contaminants from a paraffin containing feedstock. 50 hydrocarbons, including mostly paraffinic and aromatic
More particularly, the processes and systems described herein hydrocarbons, but can also containing olefinic and naph-
relate to removing contaminants from a paraffin containing thenic hydrocarbons. The kerosene boiling range fraction is
feedstock prior to the feedstock undergoing a process for usually defined as comprising a fraction having a boiling
separating the normal paraffins from the paraffin containing range of from about 149° C. (about 300° F.) to about 300° C.
feedstock. 55 (about 572° F.). The initial boiling point of the kerosene
In one aspect, a process for removing contaminants from a boiling range fraction may vary from about 149° C. (about
paraffin containing feedstock is provided that includes pro- 300° F.) to about 190° C. (about 374° F.), and the final boiling
viding a paraffin containing feedstock, passing the paraffin point may vary from about 235°C. (about 455° F.) to about
containing feedstock to an inlet of a guard bed that includes an 300° C. (about 572° F.). The kerosene boiling range generally
adsorbent material, and contacting the paraffin containing 60 includes hydrocarbons having from about 8 to about 17 car-
feedstock with the adsorbent material in the guard bed to bon atoms. The content of the normal paraffins in a kerosene
produce a treated paraffin containing feedstock. The step of boiling range petroleum fraction, can be from about 15% by
contacting can remove contaminants from the paraffin con- volume to about 35% by volume of the kerosene boiling range
taining feedstock. The process also includes removing the petroleum fraction, but is preferably greater than about 20%
treated paraffin containing feedstock from an outlet of the 65 by volume of the kerosene boiling range petroleum fraction,
guard bed, and passing the treated paraffin containing feed- and is more preferably equal to or greater than about 25% by
stock to a paraffin separation zone that separates normal par- volume of the kerosene boiling range petroleum fraction. The
 US 8,053,620 B2
3 4
kerosene boiling range petroleum fraction can be a vapor, a The guard bed 108 can have a liquid hourly space velocity
liquid, or a two-phase, vapor-liquid mixture. A two-phase, (LHSV) from about 0.5 h- 1 to about 4 h- 1 , and preferably has
vapor-liquid mixture can, for example, have from about 5 an LHSV of about 2 h- 1 .
mole percent vapor phase to about 30 mole percent vapor Contacting the paraffin containing feedstock with the
phase. adsorbent material in the guard bed 108 can remove contami-
In order to obtain a paraffin containing feedstock derived nants from the paraffin containing feedstock. Removal of
from a kerosene boiling range petroleum fraction, the kero- contaminants can be any level of removal, including a com-
sene boiling range petroleum fraction can be fractionated to plete removal, or a partial removal such as a reduction. The
produce a fractionated stream containing hydrocarbons hav- contaminants in a paraffin containing feedstock, or
ing the desired range of carbon atoms. The kerosene boiling 10
hydrotreated feedstock 104 can be, for example, undesirable
range petroleum fraction can be fractionated in any suitable
sulfur species, such as benzothiophenes and thiophenes,
manner, including, but not limited to, in a dividing wall frac-
including alkylated benzothiophenes and alkylated
tionation colunm, or in two fully thermally coupled fraction-
ation colunm, such as a prefractionator and a main column. thiophenes. In one example, the guard bed 108 can remove
In some examples, the paraffin containing feedstock is 15
thiophenic compounds by forming dimmers or trimers on the
hydrotreated prior to being passed to the inlet of the guard surface of the adsorbent material.
bed. In instances where the paraffin containing feedstock is The treated paraffin containing feedstock can be removed
derived from a kerosene boiling range petroleum fraction that from an outlet of the guard bed 108, and can be passed to a
has been fractionated, the fractionated stream is preferably paraffin separation zone 112 that separates normal paraffins
hydrotreated to produce the paraffin containing feedstock. 20 from the treated paraffin containing feedstock 110 to produce
In the example illustrated in FIG. 1, a paraffin containing a normal paraffin containing stream 114. Paraffin separation
feedstock 100, which can be a fractionated stream from a zone 112 also produces a raffinate stream 116. Raffinate
kerosene boiling range petroleum fraction, can be provided to stream 116 can include hydrocarbons, such as naphthenes,
a hydrotreating zone 102. A hydrogen containing stream 106 aromatics, and branched paraffins. Paraffin separation zone
can be introduced to the hydrotreating zone 102 and can react 25 112 can separate normal paraffins from the treated paraffin
with sulfur contaminants, nitrogen contaminants, or both, in containing feedstock by any suitable process, such as, for
the paraffin containing feedstock 100. Hydrotreating zone example, by a liquid-phase adsorptive separation process.
102 produces a hydrotreated paraffin containing feedstock Normal paraffin containing stream 114 can undergo further
104, preferably having reduced levels of sulfur contaminants, processing, such as, for example, dehydrogenation to produce
nitrogen contaminants, or both. The hydrotreating zone 102 30 an olefin containing stream, and alkylation to produce LABs.
can have any suitable arrangement, including a flow scheme, From the foregoing, it will be appreciated that although
a catalyst, and operating conditions that facilitate the removal specific examples have been described herein for purposes of
or reduction of olefins, as well as sulfur and nitrogen con- illustration, various modifications may be made without devi-
taminants. ating from the spirit or scope ofthis disclosure. It is therefore
Hydrotreated paraffin containing feedstock 104 can be to 35 intended that the foregoing detailed description be regarded
an inlet of a guard bed 108. Guard bed 108 can include an as illustrative rather than limiting, and that it be understood
adsorbent material. The guard bed 108 preferably includes a that it is the following claims, including all equivalents, that
fixed bed that includes the adsorbent material. The paraffin are intended to particularly point out and distinctly claim the
containing feedstock can be contacted with the adsorbent claimed subject matter.
material in the guard bed 108 to produce a treated paraffin 40
containing feedstock 110. What is claimed is:
The adsorbent material can include a molecular sieve mate- 1. A process for removing sulfur and nitrogen containing
rial, such as zeolites. The molecular sieve material preferably contaminants from a paraffin containing feedstock, the pro-
has an average pore size less than or equal to about 5 ang- cess comprising:
stroms. In some examples, the molecular sieve material can 45 providing a kerosene boiling range petroleum fraction;
have an average pore size of about 3 angstroms, about 4 fractionating the kerosene boiling range petroleum fraction
angstroms, or about 5 angstroms. Such molecular sieve mate- with a high bromine index to produce a liquid fraction-
rial can include, but is not limited to SGB-11, 5A-1HP, RK ated stream;
38HP, PSA adsorbent H-15, K-A, Na-A, and Ca-A. The hydrotreating the fractionated stream to produce the par-
adsorbent material can also include at least one binder. One 50 affin containing feedstock with a lower bromine index
suitable type of binder includes clay materials, such as, for compared to the bromine index of the fractionated
example, a kaolin clay, a metakaolin clay, an atapulgite clay, stream;
or a smectite clay. Preferably, the adsorbent does not cause providing the liquid paraffin containing feedstock, wherein
isomerization, or discoloration of the paraffin containing the feedstock comprises C 10 to C 13 hydrocarbons;
feedstock. In at least some examples, the adsorbent material is 55 passing the paraffin containing feedstock to an inlet of a
sacrificial, and is replaced once it is spent rather than being guard bed, wherein the guard bed includes an adsorbent
regenerated. In such examples, it is preferred that the adsor- material consisting of a molecular sieve and a binder;
bent have a useful life of up to about 3 years, or but actual contacting the paraffin containing feedstock with the
adsorbent life will be dependent upon the contaminant level. adsorbent material in the guard bed to produce a treated
The guard bed 108 can have an operation temperature of 60 paraffin containing feedstock having a reduced
from about 100° C. to about 225° C., from about 150° C. to thiophenic content relative to the paraffin containing
about 180° C. Preferably, the operation temperature of the feedstock entering the guard bed;
guard bed 108 is equal to, or within about 5° C. of the opera- removing the treated paraffin containing feedstock from an
tion temperature of the paraffin separation zone 112 that is outlet of the guard bed; and
downstream of the guard bed 108. Guard bed operation tern- 65 passing the treated paraffin containing feedstock to a liquid
peratures above about 225° C. can result in color body for- phase paraffin separation zone that separates normal
mation and discoloration of the paraffin containing feedstock. paraffins from the treated paraffin containing feedstock.
 US 8,053,620 B2
5 6
2. The process of claim 1, wherein the paraffin separation containing contaminants from the paraffin containing
zone separates normal paraffins from the treated paraffin con- feedstock and produce a treated paraffin containing
taining feedstock by a liquid-phase adsorptive separation pro- feedstock, having a reduced thiophenic content;
cess. removing the treated paraffin containing feedstock from an
3. The process of claim 1, wherein the guard bed comprises outlet of the guard bed; and
a fixed bed that includes the adsorbent material. passing the treated paraffin containing feedstock to a liquid
4. The process of claim 1, wherein the molecular sieve phase paraffin separation zone that separates normal
material has an average pore size less than or equal to about 5 paraffins from the treated paraffin containing feedstock.
angstroms. 8. The process of claim 7, wherein the paraffin containing
5. The process of claim 1, wherein the molecular sieve 10 feedstock comprises C 10 to C 13 hydrocarbons.
material comprises zeolites. 9. The process of claim 7, wherein the paraffin containing
6. The process of claim 1, wherein the binder comprises a feedstock is hydrotreated prior to being passed to the inlet of
kaolin clay, a metakaolin clay, an atapulgite clay, or a smectite the guard bed.
clay. 10. The process of claim 9, wherein the paraffin containing
7. A process for removing sulfur and nitrogen containing 15 feedstock is fractionated prior to being hydrotreated.
contaminants from a paraffin containing feedstock, the pro- 11. The process of claim 7, wherein the guard bed com-
cess comprising: prises a fixed bed that includes the adsorbent material.
providing a liquid paraffin containing feedstock derived 12. The process of claim 7, wherein the adsorbent material
from a kerosene boiling range petroleum fraction having comprises zeolites having an average pore size of about 5
a low olefin content; 20 angstroms.
passing the paraffin containing feedstock to an inlet of a 13. The process of claim 12, wherein the binder comprises
guard bed, wherein the guard bed includes an adsorbent clay.
material consisting of a zeolite and a binder;
contacting the paraffin containing feedstock with the
adsorbent material in the guard bed to remove sulfur * * * * *