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United States Patent (19) [11] 3,835,199

Schwartz, Jr. et al. (45) Sept. 10, 1974


54 DEHYDROGENATION PROCESS AND 3,267,025 8/1966 Gring et al.......................... 208/136
CATALYST 3,403, 192 9/1968 Vadekar et al.................. 260/680 E
3,585,250 6/1971 Pasternak et al................ 260/683.3
75 Inventors: Andrew K. Schwartz, Jr., Houston; 3,665,049 5/1972 Cornelius......................... 260/683.3
Tony Rabago, Jr., Pearland, both of
Tex.
73 Assignee: Petro-Tex Chemical Corporation, Primary Examiner-Delbert E. Gantz
Assistant Examiner-Juanita M. Nelson
Houston, Tex. Attorney, Agent, or Firm-N. Elton Dry
22 Filed: Apr. 24, 1972
21 Appl. No.: 246,683
57 ABSTRACT
52) U.S. Cl............ 260/683.3, 252/416, 260/680 R An improved dehydrogenation process for the produc
51 Int. Cl............................................... C07c3/28 tion of diolefins by the dehydrogenation of aliphatic
58) Field of Search......... 260/683.3, 680 R, 680 E; hydrocarbons by contacting the hydrocarbon com
252/416 pound with a catalyst containing chromic oxide, alu
mina, and a sulfur containing compound such as sulfu
56) References Cited ric acid and sulfates of zinc magnesium and cobalt.
UNITED STATES PATENTS
2,546,031 3/1951 Hanson............................... 260/680 7 Claims, No Drawings
3,835,199
1. 2
DEHYDROGENATION PROCESS AND CATALYST alumina catalysts. Further, the selectivity of the
chromia-alumina catalyst of the present invention is
BACKGROUND OF THE INVENTION
unexpectedly improved with respect to conventional
chromia-alumina catalysts. For instance, yields of bu
1. Field of the Invention tenes and butadiene from n-butane using a commercial
This application relates to the dehydrogenation of chromia-alumina catalyst (Harshaw) to which has had
aliphatic organic compounds for the production of ole added thereto small amounts of sulfuric acid were some
fins and diolefins. More particularly, this application 4.6 percent per pass greater than the corresponding
relates to improved catalytic compositions useful in the yields obtained by using the commercial catalyst (Har
preparation of butadiene and butenes from n-butane, 10 shaw) without the added sulfuric acid.
propylene from propane, isobutene from isobutane and DESCRIPTION OF THE PREFERRED
isoamylenes and isoprene from isopentane by catalytic EMBODIMENTS
dehydrogenation. According to this invention an improved catalyst and
2. Description of the Prior Art 15 a process utilizing the improved catalyst are provided
Organic compounds are commercially dehydroge for the dehydrogenation of aliphatic organic com
nated by contacting the compound to be dehydroge pounds to obtain the corresponding unsaturated deriv
nated at an elevated temperature preferably in the atives thereof.
presence of catalysts. A particularly useful catalyst 20 The process of this invention may be applied to the
which has been widely employed in preparing butadi dehydrogenation of a variety of organic compounds
ene and butylenes from n-butane is an aluminachromia having at least 2 carbon atoms to obtain the corre
catalyst. The alumina-chromic oxide catalyst is utilized sponding unsaturated derivative thereof. Such com
in a commercial process for the one-step dehydrogen pounds normally will contain from 2 to 20 carbon
ation of butane to butadiene and butenes. This process 25 atoms, at least one
has been reported to produce only about 11 mol per
cent butadiene per pass. Furthermore, the catalyst be
comes coated with coke and after a period of only sev
eral minutes, the catalyst must be regenerated by purg grouping, a boiling point below about 350°C., and
ing the catalyst bed followed by burning off of the car 30 such compounds may contain other elements in addi
bon.
In an article entitled, "Butane Dehydrogenation at tion to carbon and hydrogen such as oxygen, halogen,
Billingham,' in Chemistry and Industry, Aug. 10, 1953, nitrogen and sulphur. Preferred are compounds having
pp. 550-556, it was reported that excessive buildup of from 2 to 12 carbon atoms and especially preferred are
carbon in the alumina-chromia catalyst bed could be 35 compounds of 4 and 5 carbon atoms.
mitigated by doping the butane fed to the catalyst bed Among the types of organic compounds to be dehy
with from 30-40 ppm of carbon disulfide. It was further drogenated to the corresponding unsaturated deriva
reported in Proceedings of the National Institute of Sci tive by means of the process of this invention are ni
ences of India, volume 12, pages 97-102 (1946), that triles, alkyl halides, aldehydes, alcohols, cycloalkanes,
in the dehydrogenation of butene-1 over an alumina 40 alkanes, alkenes, and the like. Illustrative dehydrogen
chromia, the catalyst could be somewhat promoted in ations include propionitrile to acrylonitrile, propional
its activity by the addition of small amounts of sulfur dehyde to acrolein, ethyl chloride to vinyl chloride,
thereto. However, the dehydrogenation products from methyl isobutyrate to methyl methacrylate, ethane to
the sulfur modified catalyst contained detrimental ethylene, propane to propylene, isobutane to isobutyl
amounts of hydrogen sulfide. ene, n-butane to butene and butadiene-1,3, methylbu
45 tene to isoprene, cyclopentane to cyclopentene and cy
SUMMARY OF THE INVENTION clopentadiene-1,3, and the like.
According to the present invention organic, aliphatic The preferred feed to be dehydrogenated comprises
compounds are dehydrogenated by an improved pro hydrocarbons of 4 to 5 carbon atoms and particularly
cess utilizing a catalyst comprising alumina, chromium n-butane, butene-1, butene-2, pentane, pentene-1, pen
50 tene-2,
oxide and a sulfur containing compound. It has been 2-methylbutane, 2-methylbutene-1, 2
found, quite unexpectedly that when a minor amount methylbutene-2, 3-methylbutene-1, 2-methylpentane,
of a sulfur containing compound such as sulfuric acid, 2-methylpentene-1 and mixtures thereof. The pre
zinc sulfate, magnesium sulfate and cobalt sulfate are ferred products are butadiene-1,3 and isoprene.
incorporated into the alumina-chromium oxide cata 55 Diluents or stripping agents such as nitrogen, helium,
lyst, the resulting catalyst composition demonstrates or other gases may be fed to the process at any point.
significant improvements in yield of dehydrogenated Mixtures of diluents may be employed. Volatile com
products. For example, the prior art dehydrogenation pounds which are not dehydrogenated or which are de
of n-butane to butenes and butadiene using chromia hydrogenated only to a limited extent may also be pres
alumina catalyst is quite satisfactory with respect to se 60 ent as diluents.
lectivity of the products produced, however, conver The temperature during the dehydrogenation gener
sion usually falls significantly short of the thermody ally will be at least about 450°C, such as within the
namically possible equilibrium conversions. The pres range of about 500°C to about 650°C or 700°C. Prefer
ent invention provides a catalyst having a significant ably the temperatures are within the range of about
and unexpected increase in activity which results in im 65 500°C and 600°C. The total pressure during dehydro
proved and significant increase in yield of the desired genation may be atmospheric, super atmospheric or
dehydrogenation products per pass in comparison to sub atmospheric. The contact time of the organic com
the yields obtained with the conventional chromia pound during dehydrogenation may also vary widely
3
3,835,199 4.
depending upon the particular conditions employed. The alumina may be any of the known forms of alu
Determination of the optimum contact time under the mina, although preferably it is an activated alumina
particular conditions so chosen from the ranges of con such as gamma and eta alumina, so that a chromium
ditions mentioned herein is well within the skill of any oxide layer is readily deposited thereon. The alumina
artisan in this art. The flow rates will be within the 5 chromia dehydrogenation catalyst can also be prepared
range of about 0.1 to 10 liquid volumes of the organic treating activated alumina with a solution of chromic
compound to be dehydrogenated per volume of dehy acid and after drying, heating the treated activated alu
drogenation Zone containing catalyst per hour (re mina at temperatures of about 600°C. Examples of the
ferred to as LHSV). Usually, the LHSV will be between preparation of such catalyst materials are found in U.S.
0.15 and about 5. For calculation, the volume of a fixed 10 Pat. Nos. 2,399,678 and 2,419,997, the entire contents
bed dehydrogenation zone containing catalyst is that of which are incorporated herein by reference.
original void volume of reactor space containing cata The invention will be further illustrated by the fol
lyst. lowing examples. Percent conversion refers to the
The catalyst of the present invention contains acti moles of organic compound to be dehydrogenated, that
vated alumina, chromium oxide and a sulfur containing 15 is, the number of moles or organic compound con
compound. A preferred catalyst comprises a minor sumed, based on the moles of the organic compound
portion of chromium oxide and a sulfur containing being fed to the reactor. Percent selectivity refers to
compound such as sulfuric acid, cobalt sulfate, magne the moles of product formed based on the moles of or
sium sulfate and zinc sulfate with a major proportion of ganic compound consumed. Percent yield refers to the
activated alumina such as gamma or eta alumina. The 20 product formed based on the moles of organic com
catalyst generally will contain as active catalyst compo pound fed to the reactor. All other percentages are by
nents from one to forty percent chromium oxide, one weight unless expressed otherwise.
to fifteen percent sulfur containing compound with the
remainder being the activated alumina. A particularly EXAMPLES 1-3
preferred catalyst of the present invention contains as 25
active ingredients from 18 to 20 percent chromium ox The invention is illustrated in these examples by the
ide, 3 to 10 percent sulfur containing compound with dehydrogenation of n-butane to butenes and butadiene.
the remainder being gamma or eta alumina. The above In each example, the n-butane was passed through a
percentages are based on the weight of active compo catalyst bed comprising a standard alumina-chromia
nents in the catalyst, i.e., percent by weight of total 30 catalyst, obtained commercially under the trade name
chromium compounds, sulfur compounds and acti Houdry C or Harshaw CrO2 11, to which had been
vated alumina. Carriers or supports for the active cata added a specific weight percent of a sulfur containing
lyst components may be employed such as pumice, sil compound. The catalyst composition of Examples 1
ica, alpha alumina, etc. In addition, inert granular ma and 2 contained 3 weight percent and 5 weight percent
terial of high heat capacity may be mixed with the ac 35 ZnSO,7HO respectively. The catalyst composition of
tive catalyst components in predetermined amounts to Example 3 contained 5 percent by weight of H2SO4.
obtain any desired heat capacity of the complete cata The catalysts were prepared by mixing the commer
lyst bed. The selection of such an inert granular mate cially available alumina-chromia catalyst material
rial and the ratio of granular inert material to the active (Houdry C or Harshaw CrO211) with the ZnSO,7HO
catalyst components are well within the skill of an arti 40 and HSO respectively as a slurry in demineralized wa
san in the catalytic dehydrogenation art. ter. The mixed catalyst was extruded into pellets of
The catalyst compositions of the present invention about 6 inch in size and the pellets were then dried in
contain the essential ingredients of activated alumina, an oven at less than 300F. The catalyst could be cal
chromic oxide and a sulfur containing compound such 45 cined if desired, however, this is not necessary.
as sulfuric acid, cobalt sulfate, magnesium sulfate and The n-butane gas consisting almost essentially of n
zinc sulfate. These essential ingredients can be made by butane with trace amounts of isobutane and butenes
mixing the separate ingredients by any of the methods was passed through the catalyst bed at a temperature
known to those skilled in the art. For example, the alu of approximately 550°C a pressure of 22 inches mer
mina may be treated with a salt of chromium and the 50 cury vacuum and at a space velocity of 1.25 LHSV.
resulting mixture heated to decompose the salt and de The process of these examples was conducted in a cy
posit chromium oxide on the alumina. The sulfur con clic fashion wherein the n-butane was fed to the reactor
taining compound can be added to the alumina for a specified time period, the reactor was then purged
chromia component before or after the deposition of with nitrogen and then regenerated by passing air
the chromium oxide on the alumina and the resulting 55 through the catalyst bed. The cycle was then repeated.
mixture pelleted and dried, if necessary. A simple man The total time for a single cycle is as follows:
ner of preparing the catalyst of the present invention is 9 minutes feed of n-butane to the catalyst bed,
to prepare a slurry of a commercially available 1 minute nitrogen purge of the catalyst bed,
chromia-alumina catalyst such as that available under 9 minutes feed of air to the catalyst bed.
the trade name of Houdry C or Harshaw CrO21 1 and 60 The results obtained after the specified number of
adding the sulfur containing compound thereto. The hours of cyclic operation of Examples 1 and 2 are
mixture is then pelleted and dried if necessary. shown in Table I.

65
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3,835,199 6
TABLE I

Selectivity Selectivity Yield of


Total Hours Conversion to Butene to Butadiene Butene and
Example Catalyst Operation of n-Butane Production Production Butadiene
Houdry C 89 46.2 Inole % 84.4 mole % 11.3 mole % 44.2 mole %
plus 3 weight 112 453 do. 85.3 do. 10. do. 43.2 do.
percent 136 44.8 do. 86.2 do. 10.1 do. 431 do.
ZnSO7 HO -

2 Houdry C 71.5 46.3 mole % 85.8 mole % 8.8 mole % 43.8 mole %
plus 5 weight 90.5 45.9 do. 85.0 do. 9.9 do. 43.5 do.
percent 117.5 48.1 do. 84.8 do. 10.9 do. 46.0 do.
ZnSO.7HO 38.5 47.2 do. 86.6 do. 9.6 do. 45.4 do.
162.0 44.1 do. 87.5 do. 8.4 do. 423 do.
3 Houdry C 90.0 42.9 mote % 86.6 mole % 9.8 mote % 41.3 mole %
plus 10 weight 121.0 40.0 do. 86. do. 0.7 do. 38.7 do.
percent 38.5 40.3 do. 85. do. 11.0 do. 38.7 do.
ZnSO7HO

EXAMPLES 4-6 chromia component of the catalyst consisted entirely of


-- - -- chromia-alumina catalyst obtained commercially under
The dehydrogenation process of Examples 1-3 was 20 the trade name Harshaw CrO211. The results obtained
repeated with the sole exception that the alumina- in these examples are shown in Table II.
TABLE II

Selectivity Selectivity Yield of


Total Hours Conversion to Butene to Butadiene Butene and
Example Catalyst Operation of n-Butane Production Production Butadiene
4. Harshaw 5.0 21. mole % 76.1 mole % 11.7 mole % 18.6 mole %
CrO2 18.0 35.6 do. 80.9 do. 11.7 do. 33 do.
plus 5 weight 89.0 43.2 do. 82.3 do. 11. do. 40.3 do.
percent 12.0 41.3 do. 84.1 do. 0.7 do. 39.2 do.
ZnSO,7HO 136.0 40.4 do. 84.2 do. 10.4 do. 38.2 do.
5 Harshaw 66.0 46.3 mole % 83.4 mole % 9.9 mole % 43.2 mole %
CrO2 89.5 45.9 do. 85.2 do. 9.6 do. 43.5 do.
plus 5 weight 3.5 42.7 do. 83.9 do. 11.4 do. 40.8 do.
percent 137.5 43.4 do. 85.3 . do. 9.4 do. 41.1 do.
MgSO,7HO
6 Harshaw 3.5 40.3 mole % 85.3 mole % 8.4 mole % 37.7 mole %
CrO2. I 75 45.3 do. 86.4 do. 8.0 do. 42.8 do.
plus 5 weight 90.5 48.3 do. 87.3 do. 9.6 do. 46.7 do.
percent 117.5 43.8 do. 84.7 do. 9.4 do. 41.2 do.
HSO 138.5 45.9 do. 84.7 do. 10.0 do. 43.4 do.
63.0 42.7 do. 85.6 do. 9.6 do. 40.6 do.

COMPARISON EXAMPLES 7-8 catalyst obtained under the trade name Harshaw
For comparison purposes, the dehydrogenation pro- CrO211. The results obtained in these examples are
cess of Examples 1-3 and 4-6 were repeated with the 45 shown in Table III. The Houdry C and Harshaw CrO21 1
sole exception that the catalyst used in Example 7 con- catalysts were subjected to the slurry treatment in de
sisted entirely of the chromia-alumina catalyst com- mineralized water as detailed in the description of Ex
mercially obtained under the trade name Houdry C and amples 1-3, however, no other component was added
the catalyst used in Example 8 consisted entirely of the to the slurry.
TABLE II

Selectivity Selectivity Yield of


Total Hours Conversion to Butene to Butadiene Butene and
Example Catalyst Operation of n-Butane Production Production Butadiene
7 Houdry C 23.5 49.4 mole % 85 mole % 9.6 mole % 44.8 mole %
52.5 46.9 do. 85.7 do. 10.4 do. 45.1 do.
18.5 44.8 do. 85 do. 10.8 do. 42.8 do.
142.5 42.3 do. 85.2 do. 10.7 do. 4.0.1 do.
167.5 42.9 do. 83.7 do. 11.7 do. 40.9 do.
8 Harshaw 4.5 44.6 mole % 82.4 mole %. 10.2 mole % 4.2 mole %
CrO211 23.5 42.3 do. 84.1 do. 10.5 do. 40.0 do.
52.5 4.7 do. 83.6 do. 10.4 do. 39.2 do.
18.5 41.4 do. 84.9 do. 9.7 do. 39.2 do.
142.5 41.6 do. 84.9 do. 9.8 do. 39.4 do.
167.5 38.8 do. 84.2 do. 10.4 do. 36.7 do.

l
3,835,199
7 8
We claim: 2. A process according to claim 1 wherein the alu
1. A process for the catalytic dehydrogenation of or mina is gamma alumina, eta alumina or a mixture
ganic compounds having from 2 to 20 carbon atoms thereof.
and at least one 3. A process according to claim 1 wherein the or
ganic compound has between 2 and 12 carbon atoms.
4. A process according to claim 1 wherein the or
ganic compound has 4 or 5 carbon atoms.
5. A process according to claim 1 wherein the or
O ganic compound is essentially n-butane. -
6. A process according to claim 1 wherein the tem
grouping by a cyclic process wherein the catalyst is pe perature is between 500°C and 600°C and the active
riodically regenerated by oxidation which comprises catalyst consists of from 18 percent to 20 percent by
contacting said organic compound in a dehydrogen weight chromium oxide, 3 percent to 10 percent of a
ation step at a temperature of from about 450° to about 5 sulfur containing compound consisting of metal sul
700°C. with a catalyst which comprises an intimate fates, sulfuric acid and mixture thereof with the re
mixture of active catalyst components consisting essen mainder being essentially alumina.
tially of from 1 percent to 40 percent by weight chro 7. A process according to claim 1 wherein the sulfur
mium oxide, 1 percent to 15 percent of a sulfur con containing compound is selected from the group con
taining compound selected from the group consisting 20 sisting of sulfuric acid, zinc sulfate, cobalt sulfate, mag
of metal sulfates, sulfuric acid and mixtures thereof nesium sulfate and mixtures thereof.
with the remainder being essentially alumina. sk :k k : xk

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