U.S. patent number 3,816,301 [Application Number 05/268,160] was granted by the patent office on 1974-06-11 for process for the desulfurization of hydrocarbons.
This patent grant is currently assigned to Atlantic Richfield Company. Invention is credited to Harold A. Sorgenti.
United States Patent |
3,816,301 |
Sorgenti |
June 11, 1974 |
PROCESS FOR THE DESULFURIZATION OF HYDROCARBONS
Abstract
A process for reducing the sulfur content of sulfur-containing
hydrocarbon material by oxidizing at least a portion of the sulfur
in the sulfur-containing hydrocarbon material with an oxidant in
the presence of certain catalysts, for example, a
molybdenum-containing catalyst. The oxidized sulfur-containing
hydrocarbon material is further processed by means of a sulfur
reducing step to remove sulfur from the hydrocarbon material. A
hydrocarbon material having reduced sulfur content is thereafter
recovered. The preferred oxidant is tertiary butyl hydroperoxide
and the oxidation may occur in the presence of a solvent,
preferably tertiary butyl alcohol. The tertiary butyl alcohol,
which is removed from the oxidized sulfur-containing hydrocarbon
material, can be dehydrated to isobutylene and further dimerized to
form diisobutylene.
Inventors: |
Sorgenti; Harold A. (Olympia
Fields, IL) |
Assignee: |
Atlantic Richfield Company (New
York, NY)
|
Family
ID: |
23021742 |
Appl.
No.: |
05/268,160 |
Filed: |
June 30, 1972 |
Current U.S.
Class: |
208/208R;
208/240; 208/196; 208/243 |
Current CPC
Class: |
C10G
27/12 (20130101) |
Current International
Class: |
C10G
27/12 (20060101); C10G 27/00 (20060101); C10q
017/00 (); C10q 031/14 () |
Field of
Search: |
;208/196,28R,240,243 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
3565793 |
February 1971 |
Herbstman et al. |
3719589 |
March 1973 |
Herbstman et al. |
|
Primary Examiner: Davis; Curtis R.
Attorney, Agent or Firm: Uxa; Frank J.
Claims
The embodiments of the invention in which an exclusive property or
privilege is claimed are defined as follows:
1. In a desulfurization process for producing a hydrocarbon
material of reduced sulfur content wherein at least a portion of
the sulfur in a sulfur-containing hydrocarbon material is
preferentially oxidized and the oxidized sulfur-containing
hydrocarbon material is further processed by means of a sulfur
reducing step, the improvement which comprises preferentially
oxidizing said sulfur with an oxidant selected from the group
consisting of organic peroxides, organic hydroperoxides, organic
peracids, and mixtures thereof in the presence of a
molybdenum-containing catalyst prepared by a method which comprises
interacting molybdenum metal with at least one peroxy compound in
the presence of at least one saturated alcohol having from one to
four carbon atoms per molecule to solubilize at least a portion of
said molybdenum metal, said catalyst being present in an amount
sufficient to promote the preferential oxidation of said
sulfur.
2. The process of claim 1 wherein said interacting occurs at a
temperature within the range from about 25.degree.C. to about
150.degree.C.
3. The process of claim 2 wherein said catalyst is soluble in the
liquid portion of the oxidation reaction mass and is present in an
amount based on the weight of molybdenum of at least about 5 ppm.
by weight of the sulfur-containing hydrocarbon material.
4. The process of claim 1 wherein at least a major amount of said
sulfur-containing hydrocarbon material boils above about
550.degree.F.
5. The process of claim 3 wherein at least a major amount of said
sulfur-containing hydrocarbon material boils above about
550.degree.F.
6. The process of claim 5 wherein said oxidant is present in a
concentration of from about 0.1 to about 10 atoms of active oxygen
per atom of sulfur present in said sulfur-containing hydrocarbon
material.
7. The process of claim 6 wherein said oxidant is present in a
concentration of from about 1 to about 4 atoms of active oxygen per
atom of sulfur present in said sulfur-containing hydrocarbon
material.
8. The process of claim 6 wherein said catalyst is present in an
amount based on the weight of molybdenum of from about 10 ppm. to
about 500 ppm. by weight of said sulfur-containing hydrocarbon
material.
9. The process of claim 8 wherein said oxidant and said peroxy
compound are both tertiary butyl hydroperoxide, said saturated
alcohol is tertiary butyl alcohol, and said interacting takes place
in the presence of at least one primary alcohol containing from one
to about 16 carbon atoms per molecule and having at least one
primary hydroxy group present in an amount sufficient to enhance
the solubility of molybdenum.
10. The process of claim 9 wherein said oxidant is present in a
concentration of from about 1.5 to about 3.0 atoms of active oxygen
per atom of sulfur present in said sulfur-containing hydrocarbon
material.
11. The process of claim 10 wherein at least a portion of said
tertiary butyl hydroperoxide is derived from oxidation of isobutane
and said primary alcohol is a mixture of polyhydroxy alcohols which
have a molecular weight in the range from about 200 to about 300
and contain from about four to about six hydroxy groups, said
poly-hydroxy alcohols being derived from propylene epoxidation with
tertiary butyl hydroperoxide.
12. A process for producing a hydrocarbon material of reduced
sulfur-content which comprises:
1. preferentially oxidizing at least a portion of the sulfur in a
hydrocarbon material with an oxidant selected from the group
consisting of organic peroxides, organic hydroperoxides, organic
peracids and mixtures thereof in the presence of a
molybdenum-containing catalyst prepared by a method which comprises
interacting molybdenum metal with at least one peroxy compound in
the presence of at least one saturated alcohol having from one to
four carbon atoms per molecule to solubilize at least a portion of
said molybdenum metal, said catalyst being present in an amount
sufficient to promote the preferential oxidation of said
sulfur;
2. treating said oxidized sulfur-containing hydrocarbon material to
remove at least a portion of said sulfur from said hydrocarbon
material; and
3. recovering a hydrocarbon material having reduced sulfur
content.
13. The process of claim 12 wherein said interacting occurs at a
temperature within the range from about 25.degree.C. to about
150.degree.C.
14. The process of claim 13 wherein at least a major amount of said
sulfur-containing hydrocarbon material boils above about
550.degree.F. and said oxidation occurs in the presence of an added
oxidation solvent in an amount sufficient to reduce the viscosity
of the oxidation reaction mass.
15. The process of claim 14 wherein said oxidation solvent is
present in an amount such that from about 5 parts to about 2,000
parts by weight of solvent is present for every 100 parts of
sulfur-containing hydrocarbon material and said oxidant is present
in a concentration of from about 0.1 to about 10 atoms of active
oxygen per atom of sulfur present in said sulfur-containing
hydrocarbon material.
16. The process of claim 15 wherein said oxidation solvent is
tertiary butyl alcohol.
17. The process of claim 16 wherein said oxidant and said peroxy
compound are both tertiary butyl hydroperoxide and said saturated
alcohol is tertiary butyl alcohol, and said interacting takes place
in the presence of at least one primary alcohol containing from one
to about 16 carbon atoms per molecule and having at least one
primary hydroxy group present in an amount sufficient to enhance
the solubility of molybdenum.
18. The process of claim 17 wherein step (2) comprises:
A. separating at least a portion of said tertiary butyl alcohol
contained in said oxidized sulfur-containing hydrocarbon material
leaving an alcohol-poor hydrocarbon material; and
B. removing at least a portion of said sulfur from said
alcohol-poor hydrocarbon material.
19. The process of claim 17 wherein at least a major portion of
said tertiary butyl hydroperoxide is derived from oxidation of
isobutane and said primary alcohol is a mixture of poly-hydroxy
alcohol which have a molecular weight in the range from about 200
to about 300 and contain from about 4 to about 6 hydroxy groups,
said poly-hydroxy alcohols derived from propylene epoxidation with
tertiary butyl hydroperoxide.
20. The process of claim 18 comprising the additional step of
dehydrating at least a portion of said separated tertiary butyl
alcohol to form isobutylene.
21. The process of claim 20 wherein at least a portion of said
isobutylene is dimerized to form diisobutylene.
22. The process of claim 21 wherein said sulfur removal step
comprises subjecting said alcohol-poor hydrocarbon material to a
thermal treatment step.
Description
The present invention relates to an improved process for
catalytically reducing the sulfur content of hydrocarbon materials.
More particularly, the invention relates to the reduction in sulfur
content of hydrocarbon materials by the catalytic oxidation of the
sulfur impurities contained therein, followed by removal of these
oxidized impurities.
Petroleum crude oils and topped or reduced crude oils, as well as
other heavy petroleum fractions and/or distillates including vacuum
tower bottoms, atmospheric tower botttoms, black oils, heavy cycle
stocks, visbreaker product effluent and the like, are normally
contaminated by excessive concentrations of sulfur. This sulfur may
be present in heteroatomic compound which have proven difficult to
remove by conventional processing. The sulfur compounds are
objectionable, for example, because combustion of fuels containing
these impurities results in the release of sulfur oxides which are
noxious, corrosive and, therefore, present a serious problem with
respect to pollution of the atmosphere.
Many methods have been tried in attempts to remove the sulfur
compounds from hydrocarbon material. For example, U.S. Pat. No.
3,565,793 relates to a method for desulfurization of hydrocarbon
materials by oxidizing the sulfur-containing hydrocarbon with an
oxidant in the presence of a catalyst, followed by a sulfur
reducing step. However, many problems arise in trying to
catalytically oxidize the sulfur compounds in these hydrocarbon
materials. Thus, the sulfur-containing hydrocarbon material is a
complex mixture of components and includes sulfur in the form of
hetero-atomic sulfur compounds, e.g., thiophene sulfur compounds,
which are known to be difficult to remove. The oxidation of sulfur,
such as thiophene sulfur, contained in hydrocarbon material is
difficult and time consuming even when this oxidation is promoted
by a catalyst. The inability of many catalysts to provide a high
rate of reaction of sulfur oxidation is one problem involved in the
oxidative desulfurization of hydrocarbon material. Additional
problems associated with many of the prior art catalysts, include,
for example, toxicity, costs, preparation difficulties, handling
difficulties and ample availability. It would be advantageous to
provide an improved catalyst for the preferential oxidation of
sulfur in a sulfur-containing hydrocarbon material.
A further problem associated with the processing of
sulfur-containing heavy hydrocarbon materials, i.e., material the
major amount of which boils above about 550.degree.F., is the
presence of components such as asphaltenes which are difficult to
solubilize. This fact takes on added significance when the sulfur
oxidation is promoted by a homogeneous, rather than heterogeneous,
i.e., supported, catalyst system. Asphaltene solvents, such as
benzene, have been used as oxidation solvents so as to provide more
efficient contact between the sulfur-containing heavy hydrocarbon
material, the oxidant and the homogeneous catalyst system. These
extraneous solvents require additional processing to remove from
the oxidation product and thus act to reduce process efficiency.
Therefore, it would be advantageous to provide an oxidation system
in which effective contact between reactants and catalyst is
efficiently achieved.
A still further problem having to do with process efficiency is the
problem of developing a plentiful and inexpensive source of oxidant
effective to preferentially oxidize the sulfur in hydrocarbon
materials. Closely linked with this problem is the additional
concern of finding uses for the oxidant decomposition products
which result from sulfur oxidation. Therefore, it would be
advantageous to provide an efficient desulfurization process
whereby a plentiful supply of effective oxidant is produced, the
oxidant is utilized to preferentially oxidize the sulfur in
hydrocarbon material and to provide useful oxidant decomposition
product or products.
Therefore, it is an object of the present invention to provide an
improved catalyst for the oxidation of sulfur compounds in
sulfur-containing hydrocarbon materials.
Another object of the present invention is to provide an improved
process for the desulfurization of sulfur-containing hydrocarbon
materials.
An additional object of the present invention is to provide an
efficient process for producing hydrocarbon material having reduced
sulfur content utilizing the catalytic oxidation of sulfur
impurities contained in hydrocarbon material. Other objects and
advantages of the present invention will become apparent
hereinafter.
An improved process has now been discovered for reducing the sulfur
content of sulfur-containing hydrocarbon material which comprises
preferentially oxidizing at least a portion of the sulfur in the
sulfur-containing hydrocarbon material with an oxidant in the
present of a molybdenum-containing catalyst prepared by a method
which comprises interacting molybdenum metal with at least one
peroxy compound in the presence of at least one saturated aliphatic
alcohol having from one to four carbon atoms per molecule to
solubilize at least a portion of the molybdenum. The oxidized
sulfur-containing hydrocarbon material is further processed by
means of a sulfur reducing step, such as, for example, a base
treatment step, a thermal treatment step, a solvent refining step,
a hydro-desulfurization step and the like, to remove sulfur from
the hydrocarbon material. A hydrocarbon material having reduced
sulfur content is thereafter recovered.
In preparing the molybdenum-containing catalysts useful in the
present invention, metallic molybdenum is interacted, i.e.,
co-mingled or contacted, with at least one peroxy compound, e.g.,
organic hydroperoxide, organic peroxide, organic peracid, hydrogen
peroxide and mixtures thereof, in the presence of at least one low
molecular weight saturated alcohol, either mono- or poly-hydroxy,
containing from one to four carbon atoms per molecule to solubilize
at least a portion of the molybdenum metal. It is believed that the
molybdenum metal reacts with the peroxy compound to form a compound
or complex which is soluble in the saturated alcohol and remaining
peroxy compound.
Typical peroxides, hydroperoxides and peracids useful in the
preparation of the molybdenum-containing catalyst are described
hereinafter as oxidants. These peroxy compounds may also be
substituted with groups such as halides, --NH.sub.2, --SH,
##SPC1##
and the like, which do not substantially interfere with the
catalyst forming process. The most preferred peroxy compound for
use in preparing this molbdenum-containing catalyst is tertiary
butyl hydroperoxide.
Hydrogen peroxide suitable for preparing the molybdenum-containing
catalyst is preferably used in the form of an aqueous solution
containing, for example, from about 10% to about 60%, preferably
about 30 percent, by weight of hydrogen peroxide.
Typical examples of low molecular weight monohydroxy alcohols which
are suitable for use in the preparation of the present
molybdenum-containing catalyst include methyl alcohol, ethyl
alcohol, isopropyl alcohol, n-butyl alcohol, tertiary butyl alcohol
and the like. The low molecular weight polyhydroxy alcohols which
are suitable include ethylene glycol, propylene glycol,
1,2-butylene glycol and glycerol. In general, either mono- or
poly-hydroxy alcohols containing from one to four carbon atoms per
molecule are suitable. Although the presence of the lower alcohols,
e.g., methyl alcohol and ethyl alcohol, produces a faster
solubilization of molybdenum, in order to maximize the benefit of
the overall process of the present invention it is preferred that
the molybdenum metal be interacted with tertiary butyl
hydroperoxide in the presence of tertiary butyl alcohol. If
tertiary butyl alcohol is used as the saturated alcohol, it is
preferred, to enhance molybdenum solubility, that the interaction
mixture comprise at least one mono- or poly-hydroxy alcohol having
from one to about 16 carbon atoms per molecule, at least one
primary hydroxy group, and be present in an amount of from about 1
to about 25 percent by weight of the total alcohol present. A
particularly preferred alcohol mixture for use in combination with
tertiary butyl alcohol is the stream of higher poly-hydroxy
alcohols having a molecular weight in the range from about 200 to
about 300 and containing from about 4 to about 6 hydroxy groups
derived from propylene epoxidation and described in U.S. Pat. No.
3,573,226.
The relative proportions of peroxy compound and low molecular
weight saturated alcohol employed in preparing the catalyst may
vary over a broad range and is, therefore, not of critical
importance to the invention. Typically, the peroxy compound
comprises from about 5 to about 50 percent by weight of the total
peroxy compound and saturated low molecular weight alcohol used in
catalyst preparation.
The molybdenum concentration in the catalyst mixture, i.e., the
mixture comprising the dissolved or soluble molybdenum plus any
excess peroxy compound and alcohol, often is within the range from
about 15 ppm. to about 5 percent, preferably in the range from
about 1,000 ppm. to about 2 percent by weight of the total mixture.
It may be desirable to prepare the catalyst in the presence of a
solvent such as benzene, ethyl acetate and the like, in order to
obtain the optimum molybdenum concentration in the final catalyst
mixture. However, if this type of dilution is desired, it is
preferred that an excess of tertiary butyl alcohol be maintained in
the catalyst mixture for this purpose.
The molybdenum metal useful in the preparation of the present
catalyst may be in the form of lumps, sheets, foil or powder. The
powdered material, e.g., having a particle size such that it passes
through a 50 mesh sieve, preferably through a 200 mesh sieve, on
the Standard Screen Scale, is preferable since it offers increased
surface area per unit volume and an increased rate of
solubilization.
The molybdenum metal-peroxy compound interacting may be carried out
at a wide range of temperatures, for example, temperatures within
the range from about 25.degree.C. to about 150.degree.C.
Interacting pressures should be set to avoid extensive vaporization
of the peroxy compound and alcohol. Typical interacting pressures
may range from about 1 psia. to about 100 psia. In many instances,
atmospheric pressure may be used. After the interacting has been
carried out for a desired length of time, e.g., from about 5
minutes to about 30 hours, preferably from about 15 minutes to
about 6 hours, the product from the interacting may be filtered to
separate the undissolved molybdenum from the catalyst mixture which
is thereafter suitable for use as a catalyst for the oxidation of
sulfur impurities in hydrocarbon materials.
The oxidants which may be used in the oxidation step of the present
invention include organic peroxides, organic hydroperoxides,
organic peracids, and mixtures thereof. These oxidants have been
found to give excellent desulfurization when combined with the
reducing and recovery steps described herein. In addition, the use
of these oxidants have been found to be selective or preferential
for oxidation of the sulfur, that is, substantial amounts of carbon
oxidation products such as acids and ketones are not formed. In
addition, high product yields in the oxidation step, both as to the
high product yield of oxidized sulfur impurities and the high
product yield of hydrocarbon materials which remains after the
oxidation step and, in particular, after the sulfur reducing step,
are obtained utilizing the above-noted oxidants. The organic
oxidants suitable for use in the present invention, include, by way
of example, hydrocarbon peroxides, hydrocarbon hydroperoxides and
hydrocarbon peracids wherein the hydrocarbon radicals in general
contain up to about 20 carbon atoms per active oxygen atom. With
respect to the hydrocarbon peroxides and the hydrocarbon
hydroperoxides, it is particularly preferred that such hydrocarbon
radical contain from about four to about 18 carbon atoms per active
oxygen atom and more particularly from four to 10 carbon atoms per
active oxygen atom. With respect to the hydrocarbon peracids, the
hydrocarbon radical is defined as that radical which is attached to
the carbonyl carbon and it is preferred that such hydrocarbon
radical contain from one to about 12 carbon atom, more preferably
from one to about eight carbon atoms, per active oxygen atom. It is
intended that the term organic peracid include, by way of
definition, performic acid.
Typical examples of hydrocarbon radicals are alkyl such as methyl,
ethyl, butyl, t-butyl, pentyl, n-octyl and those aliphatic radicals
which represent the hydrocarbon portion of a middle distillate of
kerosene, and the like; cycloalkyl radicals such as cyclopentyl and
the like; alkylated cycloalkyl radicals such as mono- and
polymethylcyclo-pentyl radicals and the like; aryl radicals such as
phenyl, naphthyl and the like; cycloalkyl substituted alkyl
radicals such as cyclohexyl methyl and ethyl radicals and the like;
alkyl phenyl substituted alkyl radicals examples of which are
benzyl, methylbenzyl, caprylbenzyl, phenylethyl, phenylpropyl,
naphthylmethyl, naphthylethyl and the like; alkaryl radicals such
as xylyl, methylphenyl and ethylphenyl and the like radicals.
Typical examples of oxidants are hydroxyheptyl peroxide,
cyclohexanone peroxide, tertiary butyl peracetate, di-tertiary
butyl diperphthalate, tertiary butyl perbenzoate methyl ethyl
ketone peroxide, dicumyl peroxide, tertiary butyl hydroperoxide,
di-tertiary butyl peroxide, p-methane hydroperoxide, pinane
hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cumene
hydroperoxide and the like; as well as organic peracids such as
performic acid, peracetic acid, trichloroperacetic acid,
per-benzoic acid, perphthalic acid and the like.
In order to obtain the maximum benefits of the present invention,
the most preferred oxidant for use in the present invention is
tertiary butyl hydroperoxide.
The process of the present invention involves contacting a
sulfur-containing hydrocarbon material with an oxidant, for
example, of the type described above, in the presence of the above
molybdenum-containing catalyst for a time sufficient to effect the
oxidation of at least a portion of the sulfur present in the
hydrocarbon material. In general, the time required for this
oxidation to occur is from about 5 minutes to about 24 hours or
more. It is preferred that the oxidation occur in a time from about
5 minutes to about 2 hours. Because of the improved oxidation
efficiency of the present process, in a more preferred embodiment,
the oxidation takes place in a period of time from about 5 minutes
to about 25 minutes.
The catalyst is used in an amount sufficient to promote the
preferential oxidation of sulfur in a sulfur-containing hydrocarbon
material. It is preferred that the catalyst be soluble in the
liquid portion of the oxidation reaction mass and be present in an
amount based on the weight of molybdenum of at least about 5 ppm.,
more preferably from about 10 ppm. to about 500 ppm., by weight of
the sulfur-containing hydrocarbon material.
The concentration of oxidant can be from about 0.1 to about 10 or
more atoms of active, i.e., reducable, oxygen per atom of sulfur
present in the hydrocarbon material. However, it is preferred that
the oxidant be present in an amount from about 1 to about 4 atoms
of active oxygen per atom of sulfur in the hydrocarbon material. A
still more preferred oxidant concentration is from about 1.5 to
about 3.0 atoms of active oxygen per atom of sulfur. Oxidants
useful in the present invention include those having one, two or
more atoms of active oxygen per molecule of oxidant.
The more preferred oxidant concentration range, i.e., from about
1.5 to about 3.0 active oxygen atoms per atom of sulfur, is of
value if the oxidant decomposition product, for example, an alcohol
in the case of hydroperoxide oxidant, is to be stripped from the
hydrocarbon material after oxidation and used for different
productive purposes. For example, if essentially pure, i.e.,
contaminated by no other peroxy compounds, tertiary butyl
hydroperoxide is used as the oxidant, the decomposition product,
i.e., tertiary butyl alcohol, can be separated from the hydrocarbon
material and used to improve the quality of unleaded gasoline.
However, in order to be useful as a gasoline improver, the tertiary
butyl alcohol must be essentially free, i.e., less than about 100
ppm., of tertiary butyl hydroperoxide. It has been found that by
providing an essentially pure tertiary butyl hydroperoxide oxidant
in a concentration from about 1.5 moles to about 3.0 moles per mole
of sulfur in the hydrocarbon fraction, a product stream of tertiary
butyl alcohol, essentially free of excess oxidant can be obtained
by stripping the alcohol from the hydrocarbon material after
oxidation. Oxidant concentrations in excess of about 3.0 moles per
mole of sulfur may result in oxidant carry over into the
decomposition product stream thereby causing additional processing
of this stream to eliminate the oxidant. This useful tertiary butyl
alcohol product is obtained without sacrificing the substantial
oxidation benefits of the invention.
Additional and distinct advantage flow from using oxidant
concentration in the more preferred range regardless of oxidant
purity. Included among these advantages are the efficient
utilization of oxidant without sacrificing the substantial
oxidation benefits of the present invention and a further
minimizing of side reactions, e.g., carbon oxidation, during the
oxidation step, thus improving the yield and quality of the final
reduced sulfur hydrocarbon material.
The oxidation step of the present invention may be carried out over
a wide range of temperatures, for example, from about 25.degree.F.
to about 450.degree.F. and preferably from about 50.degree.F. to
about 300.degree.F. The oxidation may be carried out at pressures
ranging, for example, from about 1 atmosphere to about 100
atmospheres or more.
Many types of apparatus are suitable for carrying out the oxidation
including rocking autoclave, mechanically stirred tanks, etc. The
reactions can be carried out batch-wise, semi-continuously or
continuously.
Before subjecting the hydrocarbon material to the sulfur reduction
step, it is preferred to separate out the oxidant decomposition
product or products, oxidation solvent, if any, and the alcohol or
alcohols from the catalyst mixture. This separation can be obtained
using conventional techniques, for example, simple distillation
and/or stripping the hydrocarbon material during or after oxidation
with a gas such as carbon dioxide or nitrogen.
In carrying out the process of this invention, a sulfur reduction
step is utilized in combination with the oxidation step. A brief
description of typical sulfur reduction steps is given below.
In the base treatment sulfur reducing step, the oxidized
sulfur-containing hydrocarbon material is contacted with a base,
preferably an alkali metal hydroxide, for a time sufficient to
reduce the sulfur content of the hydrocarbon material, generally
from about 10 minutes to about 24 hours, preferably from about 1
hour to about 6 hours. The reaction temperature is generally from
about 300.degree.F. to about 900.degree.F., preferably from about
400.degree.F. to about 750.degree.F. In addition, pressures above
atmospheric can be utilized in carrying out the base treatment.
Thus, for example, pressures up to 100 atmospheres can be utilized
in carrying out the base treatment. In general, it is preferred to
use an alkali metal hydroxide, preferably potassium or sodium
hydroxide, although the alkaline earth metal hydroxides or oxides,
calcined dolomitic materials and alkalized aluminas can be utilized
in carrying out the base treatment. In addition, mixtures of
different bases can be utilized. In general, an aqueous solution of
the base at a concentration on a mole basis of generally from about
1 mole of base to 1 mole of sulfur up to about 4 moles of base per
mole of sulfur is utilized.
In the thermal treatment step, sulfur reduction is accomplished by
treating the oxidized sulfur at temperatures above 300.degree.F.,
preferably above 500.degree.F. and particularly in the temperature
range of from about 550.degree.F. to about 900.degree.F. for a
period sufficient to ensure that substantially all the sulfur
gaseous decomposition products are removed. This period of time in
general is within the range from about 30 minutes to about 10
hours, preferably in the range from about 30 minutes to about 5
hours. Under these conditions, the oxidized sulfur compounds are
decomposed and the sulfur is liberated mainly as SO.sub.2 although
at higher temperatures in the region of 550.degree.F. and over,
increasing quantities of H.sub.2 S are also liberated. The thermal
decomposition step may be carried out in the presence of suitable
promoting materials comprising porous solids having acidic or basic
properties for example, ferric oxide on alumina, bausite, thoria on
pumice, silica-alumina, soda-lime and acid sodium phosphate on
carbon. Preferably, in the thermal decomposition step, a small
quantity of an inert carrier gas, for example, nitrogen, is passed
through the reaction mixture to avoid local overheating and also to
remove the gaseous sulfur decomposition products.
The catalytic hydrodesulfurization step may be carried out under
relatively mild conditions in a fixed, moving, fluidized or
ebullating bed of catalyst. Preferably, a fixed bed of catalyst is
used under conditions such that relatively long periods elapse
before regeneration becomes necessary, for example, a temperature
within the range of from about 500.degree.F. to about
900.degree.F., preferably from about 650.degree.F. to about
800.degree.F., and at a pressure within the range of from about 100
psig. to about 3,000 psig. or more.
A particularly preferred pressure range within which the
hydrodesulfurization step provides extremely good sulfur removal
while minimizing the amount of pressure and hydrogen required for
the hydrodesulfurization step are pressures within the range of
about 300 psig. to about 800 psig., more preferably from about 400
psig. to about 600 psig.
This invention involves the processing of various sulfur-containing
hydrocarbon materials, such as those derived from petroleum
sources. In general, the sulfur content of these materials may be
greater than about 1 percent by weight. In many instances these
hydrocarbon materials contain a significant amount of thiophene
sulfur which is known to be difficult to remove. Examples of
hydrocarbon materials which are particularly suited to the present
process include heavy hydrocarbon materials such as petroleum
fractions containing at least a major amount of material boiling
above about 550.degree.F., for example, crude oil and atmospheric
and vacuum residues which contain about 1 percent by weight or more
of sulfur. Additional examples of suitable hydrocarbon materials
include cracked gas oils, residual fuel oils, topped or reduced
crudes, crude petroleum from which the lighter fractions are
absent, residues from cracking processes and sulfur-containing
hydrocarbon materials from tar sands, oil shale and coal. The
invention is especially suited to those sulfur-containing heavy
hydrocarbon materials which cannot be deeply flashed without
extensive carry over of sulfur-containing compounds. Typical
examples of the 2,3,4, and 5-ring thiophene-containing materials
found in heavy hydrocarbon materials which are difficult to remove
include benzothiophene, dibenzothiophene, 5-thia-3,4-benzofluorene,
tetraphenyl-thiophene, diacenaphtho (1,2-b,1', 2'-d) thiophene and
anthra (2,1,9-cde) thianaphthene. The hydrocarbon material may also
contain non-thiophene sulfur, various sulfides, and elemental
sulfur which can be removed by the process of the present
invention.
As noted previously, the preferred oxidation catalyst for use in
the present invention is prepared using a combination of molybdenum
metal, tertiary butyl hydroperoxide and tertiary butyl alcohol.
Also, the preferred oxidant for use is tertiary butyl
hydroperoxide. In a particularly preferred embodiment of the
present invention, it has been discovered that tertiary butyl
hydroperoxide and tertiary butyl alcohol resulting from isobutane
oxidation can be used in the process of this invention without
requiring any other significant processing, e.g., purification
step.
In this process, isobutane is oxidized to give a mixture of
tertiary butyl hydroperoxide and tertiary butyl alcohol by various
methods. For example, isobutane can be oxidized noncatalytically in
the liquid phase with a free oxygen-containing gas, such as
molecular oxygen and using reaction temperatures, for example, in
the range from about 100.degree.C. to about 150.degree.C. and
pressures above about 400 psig. It has been discovered that the
complex isobutane oxidation product mixture comprising tertiary
butyl hydroperoxide, tertiary butyl alcohol and small amounts,
e.g., less than about 5 percent by weight each, of various other
components such as acetone, water, carbon dioxide, formic acid,
methanol, isobutanol, etc., can be used, without further
significant processing, as the source of at least a major portion,
preferably at least about 80 percent by weight and more preferably
essentially all, of the tertiary butyl hydroperoxide used as
oxidant and peroxy compound in the present invention without
sacrificing oxidation efficiency. In addition, a portion of this
isobutane oxidation product mixture may be used to prepare the
molybdenum-containing catalyst in situ, e.g., in the presence of
the sulfur-containing hydrocarbon material.
In this preferred process embodiment, the tertiary butyl alcohol in
the complex product mixture from isobutane oxidation promotes the
sulfur oxidation by reducing the viscosity of the oxidation
reaction mass. When tertiary butyl alcohol is used as an oxidation
solvent in the present process, from about 5 parts to about 2,000
parts, preferably from about 50 parts to about 2,000 parts, more
preferably from about 50 parts to about 1,000 parts, by weight of
alcohol is present per 100 parts of sulfur-containing hydrocarbon
material. Quite unexpectedly, the use of this alcohol as a solvent
in the oxidation step produces the same reaction efficiency and
degree of desulfurization as when a more inclusive aromatic
hydrocarbon solvent, such as benzene, is used. Using tertiary butyl
alcohol rather than an extraneous oxidation solvent has a
substantial processing benefits, e.g., the tertiary butyl
hydroperoxide-alcohol-containing mixture from isobutane oxidation
can be used without further processing to remove the alcohol. In
addition, no solvent other than tertiary butyl alcohol need be
removed from the hydrocarbon material after sulfur oxidation.
At least a portion of the tertiary butyl alcohol product from the
sulfur oxidation step can be dehydrated to isobutylene which can be
dimerized to form diisobutylene. The latter has many uses, for
example, as an octane improver in gasoline.
The tertiary butyl alcohol dehydration may be carried out using
conventional procedures. The dehydration may take place in the
liquid, vapor or mixed liquid-vapor phase and is preferably
catalyzed. Included among the catalysts which are known to promote
the dehydration of alcohols such as tertiary butyl alcohol are
acidic catalysts such as various Bronsted and Lewis Acids; silica,
alumina and silica-alumina based solid acids; sulfuric acid; acidic
ion exchange resins; acidic zeolites and the like. If the tertiary
butyl alcohol dehydration is to be carried out in the vapor phase,
reaction temperatures may range from about 200.degree.F. to about
800.degree.F., preferably from about 250.degree.F. to about
600.degree.F. while reaction pressures may range from about
atmospheric pressure to about 500 psig. Liquid phase alcohol
dehydration may be carried out at a temperature in the range from
about 20.degree.F. to about 300.degree.F., preferably from about
100.degree.F. to about 250.degree.F., at a pressure sufficiently
high to maintain the liquid phase in the reactor, e.g., typically
in the range from about atmospheric pressure to about 1,000 psig.
or higher. When a heterogeneous dehydration catalyst is employed,
the weight hourly space velocity may vary over a broad range
depending on the other reaction conditions and conversions desired.
Typically, the dehydration reaction is carried out at a weight
hourly space velocity in the range from about 1 to about 30,
preferably from about 2 to about 10.
As stated above, the isobutylene can be dimerized to form
diisobutylene, by any one of a number of procedures well known in
the art. The isobutylene dimerization may be made to occur in the
liquid vapor or mixed liquid-vapor phase and is preferably
catalyzed. Among the catalysts which are useful in the dimerization
reaction are Bronsted acids; sulfuric acid; phosphoric acid;
silica, alumina and silica-alumina based solid acids; acidic ion
exchange resins and the like, as well as Ziegler-Natta catalysts
and transition metal complex catalysts. If the dimerization is to
be carried out in the vapor phase, the reaction temperature may
range from about 0.degree.F. to about 450.degree.F., preferably
from about 40.degree.F. to about 400.degree.F., at a pressure in
the range from about atmospheric pressure to about 300 psig. or
more. If a liquid phase reaction is desired, typical dimerization
temperatures range from about 0.degree.F. to about 450.degree.F. at
a pressure sufficient to maintain the reactant in the liquid phase,
e.g., from about atmospheric pressure to about 1,000 psig. or more.
When a heterogeneous catalyst is employed in the dimerization
reaction, the weight hourly space velocity is typically in the
range from about 1 to about 50, preferably from about 20 to about
30.
Following the sulfur oxidation step the hydrocarbon material is
sent to a sulfur removal step such as that described previously.
Conventional procedures, e.g., flashing, stripping, distillation
and the like may be employed to recover a hydrocarbon material
having reduced sulfur content.
The following examples illustrate more clearly the process of the
present invention. However, these illustrations are not to be
interpreted as specific limitations on the invention.
EXAMPLE I
This example illustrates the desulfurization of a heavy hydrocarbon
material.
The hydrocarbon material employed was a benzene soluble petroleum
vacuum still residuum (Initial Boiling Point 610.degree.F., 15
percent overhead - 962.degree.F.) having the following
composition.
______________________________________ Weight %
______________________________________ Sulfur 3.13 Nitrogen 0.45
Carbon 85.38 Hydrogen 10.43 Oxygen 0.83
______________________________________ *The proportions listed here
result from a series of independent chemical analyses and,
therefore, the sum of the weight percents is slightly in excess of
100.
A soluble, i.e., homogeneous, oxidation catalyst was prepared by
combining 0.74 weight percent molybdenum powder with tertiary butyl
hydroperoxide in the presence of tertiary butyl alcohol and a
mixture of C.sub.10 to C.sub.15 gylcols containing from 4 to 6
hydroxyl group per molecule wherein at least one of the hydroxyl
groups was primary. The weight ratio of tertiary butyl
hydroperoxide to tertiary butyl alcohol to glycols was about
2.1:4:1. This combination was heated to reflux temperature with
constant stirring and maintained at this temperature until all the
molybdenum had dissolved.
Tertiary butyl hydroperoxide was used as the oxidant to oxidize the
sulfur impurities in the hydrocarbon material. This oxidant was
used in the form of a commercially available mixture containing
about 90 percent tertiary butyl hydroperoxide. Benzene was used as
a solvent in the oxidation reaction and amounted to about 50
percent by weight of the oxidation reaction mixture.
The oxidation reaction mixture was formed by combining the
hydrocarbon material, benzene catalyst and tertiary butyl
hydroperoxide with constant stirring to insure uniformity. This
mixture contained 3.6 moles of tertiary butyl hydroperoxide per
mole of sulfur and 187 ppm. of molybdenum.
200 grams of this reaction mixture was placed in a glass reaction
flask equipped with heating means, stirrer and a water-cooled
condenser. The flask was heated to about 75.degree. to 81.degree.C.
which caused the reaction mixture to reflux. This temperature was
maintained for 16 hours to effect sulfur oxidation. After this
period of time, the product in the flask was stripped free of
essentially all benzene, tertiary butyl alcohol from tertiary butyl
hydroperoxide decomposition and lighter components.
The remaining hydrocarbon product was cooled and placed in a glass
vessel which itself was in a salt bath. This material was heated to
a temperature within the range from 750.degree.F. to 800.degree.F.
and maintained at this temperature for 4 hours. Throughout this
period of time, hydrogen gas at atmospheric pressure was sent
through the glass vessel. At the end of 4 hours, the liquid product
was sampled and analyzed for sulfur content. It was determined that
the above processing had removed about 50 percent of the sulfur
which was originally contained in the vacuum residuum.
EXAMPLE II
This example illustrates the desulfurization of a heavy hydrocarbon
material using tertiary butyl alcohol rather than benzene as
solvent.
The hydrocarbon material used was the same as the benzene soluble
petroleum vacuum still residuum employed in Example I. The
oxidation catalyst used was prepared in the same manner and had the
same composition as the catalyst used in Example I. Tertiary butyl
hydroperoxide was used as oxidant and tertiary butyl alcohol,
amounting to about 50 percent by weight of the oxidation reaction
mixture, was used as oxidation solvent.
The tertiary butyl hydroperoxide employed as an oxidant in this
example was the product of liquid phase, noncatalytic oxidation of
isobutane. Thus, the tertiary butyl hydroperoxide used was present
in a mixture of 42.1 percent by weight tertiary butyl
hydroperoxide, about 52 percent by weight tertiary butyl alcohol
and 5.9 percent by weight of other impurities such as, acetone,
water, carbon dioxide, formic acid, methanol and isobutanol.
The oxidation reaction mixture was formed by combining the
hydrocarbon material, tertiary butyl alcohol solvent, catalyst and
tertiary butyl hydroperoxide with constant stirring. It was
determined that not all of the hydrocarbon material was soluble in
the tertiary butyl alcohol. This mixture contained 3.6 moles of
tertiary butyl hydroperoxide per mole of sulfur and 80 ppm. of
molybdenum.
This reaction mixture was placed in equipment similar to that
described in Example I and heated to a temperature of about
82.degree.C. which caused the reaction mixture to reflux. This
temperature was maintained for 7.5 hours to effect sulfur
oxidation. After this period of time, the product was stripped free
of essentially all tertiary butyl alcohol and lighter
components.
The remaining hydrocarbon product was cooled and placed in a glass
vessel similar to that described in Example I. This product was
heated to a temperature within the range from 734.degree.F. to
750.degree.F. and maintained at this temperature for 2 hours.
Throughout this period of time, hydrogen gas at atmospheric
pressure was sent through the glass vessel. At the end of two
hours, the liquid product was sampled and analyzed for sulfur
content. It was determined that the above processing had removed
about 50 percent of the sulfur which was originally contained in
the vacuum.
The above examples illustrate a number of the substantial benefits
of the present invention. For instance, both Examples I and II show
desulfurization using the improved oxidation catalyst disclosed
herein. In addition, this catalyst provides for an improved rate of
oxidation and thus can make possible reduced reaction times for the
sulfur oxidation of the present invention.
Furthermore, Examples I and II illustrate the surprising discovery
that tertiary butyl alcohol, admittedly a less inclusive solvent
than benzene for certain components of heavy hydrocarbon materials,
is as effective as benzene when used as solvent for oxidation of
sulfur-containing heavy hydrocarbon material. The use of tertiary
butyl alcohol as oxidation solvent has significant and substantial
benefits, particularly when tertiary butyl hydroperoxide is used as
oxidant. As tertiary butyl hydroperoxide is decomposed, tertiary
butyl alcohol is formed. This decomposition product, i.e., tertiary
butyl alcohol, must be removed from the final hydrocarbon product
of reduced sulfur content. If benzene is used as oxidation solvent,
additional processing equipment may be necessary to separate the
benzene from the decomposition product tertiary butyl alcohol.
However, if the oxidation solvent and oxidant decomposition product
are one and the same compound, i.e., tertiary butyl alcohol,
additional processing required to recover useable and/or saleable
products is minimized. This processing benefit can be taken
advantage of because of the discovery that tertiary butyl alcohol
performs as well as benzene as an oxidation solvent in the present
invention.
Examples I and II illustrate an added benefit of the present
process. Example II, when compared to Example I, demonstrates that
impure tertiary butyl hydroperoxide obtained from isobutane
oxidation may be used as oxidant without adversely affecting the
sulfur oxidation of the present invention. Thus, tertiary butyl
hydroperoxide derived from isobutane oxidation may be used as
oxidant rather than pure or near pure tertiary butyl hydroperoxide,
such as used in Example I.
While this invention has been described with respect to various
specific examples and embodiments, it is to be understood that the
invention is not limited thereto and that it can be variously
practiced within the scope of the following claims.
* * * * *