GB2162082A - Improved catalyst for hydrocarbon dehydrogenation - Google Patents

Improved catalyst for hydrocarbon dehydrogenation Download PDF

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Publication number
GB2162082A
GB2162082A GB08518705A GB8518705A GB2162082A GB 2162082 A GB2162082 A GB 2162082A GB 08518705 A GB08518705 A GB 08518705A GB 8518705 A GB8518705 A GB 8518705A GB 2162082 A GB2162082 A GB 2162082A
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alumina
carrier
solution
carried out
catalyst
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GB8518705D0 (en
GB2162082B (en
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John Francis Kirner
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Air Products and Chemicals Inc
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Air Products and Chemicals Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Improved conversion of paraffin and higher yield of desired dehydrogenated product are obtained in the dehydrogenation of C3 to C5 paraffins over a chromia-alumina catalyst, when using a catalyst prepared by spraying the alumina carrier with a soluble chromium compound to incipient wetness, instead of conventionally soaking the alumina carrier with excess chromium solution. The method is of particular use in conversion of isobutane to isobutylene.

Description

SPECIFICATION Improved Catalyst for Hydrocarbon Dehydrogenation The present invention relates to the catalytic dehydrogenation of C3-C6 hydrocarbons and is particularly concerned with the production of improved catalyst for use in such process.
The production of olefins by catalytic dehydrogenation of the corresponding paraffins, more particularly dehydrogenation of C3 to C5 paraffins, is well known in the art and certain of such process are in commercial practice. In typical commercial practice the catalyst generally employed is chromium oxide (Cr203) deposited on an alumina support, which support may consist essentially of alumina of the gamma, eta or chi phase type.
Most widely used among commercial dehydrogenation operations is that known as the Houdry Catadiene Process, designed originally for the production of butadiene from butane, to meet requirements for synthetic rubber. The process is described in numerous technical publications including the recent article by Craig, R. G., etal. in Chemical Engineering Progress, February 1979 at pages 62-65. This process is an adiabatic, fixed-bed, multi-reactor type wherein the C4 charge stock is dehydrogenated over catalyst comprised of active alumina impregnated with 120% chromic oxide.
For the manufacture of C3 to C5 mono-olefins the related CATOFIN process was developed, operating under conditions comparable to that of the earlier CATADIENE process. In the CATOFIN process, a single C3-C5 paraffin or a mixed hydrocarbon feedstock in charged. An important aspect of the process is the conversion of isobutane to isobutylene, which iso-olefin can be reacted with methanol to produce MTBE (methyl-tertiary-butyl-ether) for use as a high octane gasoline blending component.Typical conditions advocated for production of C3-C5 mono-olefins from the corresponding saturated hydrocarbons, includes temperatures in the range of 1,000 to 1400"F (53-760"C), at subatmospheric pressures of 250--500 mm Hg. absolute and at space velocity below 1 (vlhriv) employing catalyst comprising 1 25 percent Cr203 (by weight of catalyst) on an alumina support. Production of C3-C5 mono-olefins is described in Hydrocarbon Processing of November 1983 at page 117.An extensive discussion of the history and development of catalytic dehydrogenation for production of mono- and di-olefins is found in Advances in Petroleum Chemistry and Refining. (Interscience Publishers, N.Y. 1961), vol.4, Chapter 10 (beginning at page 451), of which pages 479--485 are here of more pertinent interest. An article by Gussow, S., etal. in Oil and Gas Journal, December 8, 1980, pages 96101, further describes the Houdry CATOFIN process for C5 and C4 mono-olefin production, and process layouts for conversion of obtained isobutylene to MTBE.
Chromia on alumina catalysts for use in dehydrogenation of hydrocarbons are generally prepared by soaking granules or pellets of the substrate in a solution of the chromium compound in excess of the volume required to cover the pellets, said solution containing the desired concentration of soluble chromium compound. Following impregnation with the chromium solution the pellets are drained to remove the excess solution, dried and calcined.
While satisfactory performance was obtained in dehydrogenation processes employing available commercial chromia-alumina catalyst having 1525% Cr203 by weight, typically 1820% Cr203, over the years attempts were made with greater or less success to improve the useful life of the catalyst and/or to improve one or more catalyst properties, such as activity, selectivity and attrition resistance. Among the patented processes directed to the production of improved chromia-alumina dehydrogenation catalysts are the following: U.S. Patent 2,945,823 describes improving the stability of chromia-alumina catalyst by incorporation therein of 0.5 to 2.0% sodium bentonite.The pelleted alumina substrate containing the incorporated bentonite stabilizer is impregnated with aqueous chromic acid solution by the usual prior art "excess solution" technique--that is by soaking the pellets in an amount of the chromic acid solution greater than that which can be sorbed by the pellets, after which the pellets are drained to remove the excess solution.
U.S. Patent 2,956,030, companion to the above '823 patent, also discloses incorporation of sodium bentonite in the alumina support but employs a somewhat different technique in forming the substrate into which the chromic acid solution is incorporated by sorption. The patent discloses, in addition, that the presence of alkali metal ion in the catalyst within certain narrow limtis has a beneficial effect. The optimum Na2O content advocated is in the range of 0.25 to 0.45%.
While the use of the "excess solution" technique was that mostly advocated and chiefly employed in the commercial manufacture of chromia-alumina dehydrogenation catalyst, in some instances, such as those in which other metals or metal oxides in substitution for or addition to chromium oxide were incorporated in the carrier, the so-called "no excess solution" technique was used, otherwise referred to as "capacity absorption" technique. Such method is disclosed in U.S. Patent 3,272,760 for the preparation of dehydrocyclization catalyst, which comprises an alumina carrier incorporating 0.1 to 2% chromium and 0.2 to 5% of a noble metal of the platinum group.
It has now been found that chromia-alumina catalyst having improved activity and selectivity, particularly for dehydrogenation of isobutane, can be prepared by spray impregnation of the alumina support with the chromium compound only to incipient wetness, followed by customary drying and calcining.
The accompanying figure of drawing is a series of graphs showing the mol.% iC4 conversion as abscissa and mole.% selectivity C4 as ordinates, in which curve A is a plot of the results obtained with conventional chromia-alumina catalyst and curve B the results obtained with a catalyst prepared according to the present invention.
The following example describes the preparation of a chromia-alumina (Cr2O3lAl2O3) dehydrogenation catalyst in accordance with the present invention.
EXAMPLE 170 ml of an aqueous solution of CrO3 (80 g CrO3/100 ml solution) and 1 ml of NaOH solution (0.3 g NaOH/1 ml solution), was diluted to 205 ml with distilled water. (This diluted chrome solution was that calculated to fill about 90% of the pore volume of the alumina support). The diluted solution was sprayed on 500 g of eta alumina 1/8 inch pellets over a period of 5 minutes, using a rotary spray impregnator in which the alumina pellets were held in an angled fluted glass beaker, which was rotated while the solution was pumped through a glass wand provided with small pinholes through which the solution was directed onto the tumbling pellets. After all of the solution was sprayed, tumbling was continued for an additional five minutes.
The impregnated pellets were then dried for 2 hours at 2500F (120 C) with through air circulation, followed by heat treatment in a muffle furnace at 1200"F (650"C) for 2 hours and treatment in flowing 20% steam80% air for 4 hours at 760 C.
The support employed for the obtained catalyst had the following physical properties: Surface Area: 150 m2/g Bulk Density: 0.836 kg/liter Porosity: 61 cc/100 ce support % H2O Absorption: 45 g H20/100 g support Pellet Density: 1.36 gfcc True Density: 3.53 glcc Total Pore Volume: 0.435 cc/g Avg. Pore Diameter: 0.011 microns The obtained catalyst had a calculated chromium content of about 17% Cr203 by weight.
Preparation of the catalyst of the invention is not limited to the use of eta alumina substrate. Other forms of alumina may be employed, such as gamma orchi. Also, instead of CrO3 other soluble Cr salts or compounds may be employed, such as chromic nitrate, acetate, etc.
The spray impregnation of the support is preferably done at room temperature, but generally temperatures in the range of 10--90"C are satisfactory. The spray time is not particularly critical and may be carried out generally in the time range of 2-15 minutes, preferably in about 5 minutes.
The amount and concentration of the chromium-containing solution employed for impregnating the alumina support depends, of course, on the desired quantity of Cr203 sought to be deposited on the substrate. The preferred range for dehydrogenation of C4 hydrocarbons is in the range of about 1525% Cr2O3 by weight of Al203, 17 to 19% being most preferred. The impregnating solution should best contain a small amount of alkali in the order of up to about 0.5 wt.%. The total volume of solution should be that needed to fill 75105% of the pore volume of the support, preferably about 90% thereof.
Drying of the impregnated pellets may be carried out at temperature in the range of 212--350"F (100 to 180 C), preferably at about 250"F (120"C) for about 2 hours. Subsequent heat treatment of the dried catalyst may be effected in 2-6 hours at a temperature in the range of 120-1470"F (650--800"C), preferably at about 760"C (1400 F) for 4 hours.
For the dehydrogenation of isobutane to isobutylene the same operating conditions may be employed using the catalyst of the invention as those previously recommended for use with conventional chromia-alumina catalyst. Typically these dehydrogenation conditions comprise temperature in the range of 540--650"C at an isobutane partial pressure of up to about 0.5 atmospheres and at a gas hourly space velocity (GHSV) of 1 44O2880, charging the iC4 with or without an inert carried gas. Typical preferred operation is at temperature in the range of 580--620"C and 2160 GHSV, charging about 17% iC4 in helium or other inert carrier gas.
EXAMPLE 2 a) A series of runs were carried out at preferred conditions using the catalyst of Example 1 for dehydrogenation of 17% isobutane in helium at selected temperatures, atmospheric pressure and at GHSV of 2160. The products obtained during 10 minute on-stream periods were analyzed. The results are shown in Table 1 below.
b) For comparison with the runs made in Example 2(a) another series of runs were carried under the same conditions but employing standard Cr2O3-Al203 catalyst prepared by excess solution technique.
These results are also shown in Table 1.
Prior to testing at each temperature, the catalyst was treated in flowing air at 120 cc/min for 30 minutes at 650"C and then with H2 flowing at 240 cc/min at 650"C, at a GHSV of 1440.
TABLE 1 iC4 iC4= iC4= C1-C3 Coke Temp Mol % Mol % Mol % Mol % Mol % Catalyst "C Conv Yield Selec Selec Selec Example 1 580 54 51.8 96 2 1 600 62 57 92 3 2 620 70 59.5 85 6 6 Standard 580 42 40.3 96 2 1 600 48 44.2 92 3 4 620 58 47 81 6 11 The comparison of selectivity vs. conversion is shown by the plots in the drawing, where curve A represents plotted results with the standard Cr203-AI203 catalyst and curve B the results obtained using catalyst prepared in accordance with the invention (Ex. 1).
Selectivity is calculated on the basis of mol.% of isobutylene in the conversion products formed.
It will be seen from the above reported results that the catalyst prepared by spray impregnation to incipient wetness is superior in performance to that prepared by conventional excess solution techniques, in both activity and selectivity at conventional operating conditions.
While the advantages displayed by catalyst prepared in accordance with the invention is shown above in connection with the conversion of isobutane to isobutylene, it will be understood that the catalyst can be beneficially employed in the dehydrogenation of other C3-C5 hydrocarbons, at the operating conditions heretofore advocated using typical commercial chromia-alumina dehydrogenation catalyst.

Claims (40)

1. A method of dehydrogenation of C3-C5 hydrocarbons over a chromia-alumina catalyst under conditions for the production of mono-olefins, wherein said catalyst has been prepared by spraying the alumina carrier with a solution of a soluble chromium compound to incipient wetness, followed by drying and heat treating.
2. A method as claimed in Claim 1, wherein said solution of soluble chromium compound has been sprayed in an amount needed to fill 75% to 105% of the pore volume of the alumina carrier.
3. A method as claimed in Claim 2, wherein said solution has been sprayed in an amount needed to fill about 90% of the pore volume of the alumina carrier.
4. A method as claimed in any one of the preceding claims, wherein said soluble chromium compound has been sprayed in an amount required to deposit 15 to 25% Cr203 in said carrier.
5. A method as claimed in Claim 4, wherein said soluble chromium compound has been sprayed in an amount required to deposit 1719% Cr2O3 in said carrier.
6. A method as claimed in any one of the preceding claims, wherein the said solution contained up to 0.5 wt% alkali.
7. A method as claimed in any one of the preceding claims, wherein the spray impregnation was carried out at 10 to 900C.
8. A method as claimed in Claim 7, wherein the spray impregnation was carried out at room temperature.
9. A method as claimed in any one of the preceding claims, wherein the spray impregnation was carried out in 2 to 15 minutes.
10. A method as claimed in Claim 9, wherein the spray impregnation was carried out in about 5 minutes.
11. A method as claimed in any one of the preceding claims, wherein said drying was at 100 to 180"C (212--350"F).
12. A method as claimed in Claim 11,wherein said drying was at about 120"C (250"F) for about 2 hours.
13. A method as claimed in any one of the preceding claims, wherein said heat treatment was at 650 to 800"C (1200--1470"F) for 2 to 6 hours.
14. A method as claimed in Claim 13, wherein said heat treatment was at about 760"C (1400"F) for 4 hours.
15. A method as claimed in any one of the preceding claims, wherein said carrier consists essentially of eta alumina.
16. A method as claimed in any one of the preceding claims, wherein the feed hydrocarbon comprises isobutane.
17. A method as claimed in Claim 16, wherein said dehydrogenation is carried out at atmospheric pressure and at a temperature in the range of 54650"C and at a space rate of 144O288()GHSV.
18. A method as claimed in Claim 17, wherein the dehydrogenation temperature is in the range of 58620"C and the space rate is about 2160 GHSV.
19. A method as claimed in Claim 17 or Claim 18, wherein the isobutane charged with an inert carrier gas.
20. A method as claimed in Claim 19, wherein said inert gas is helium.
21. A method as claimed in any one of Claims 1 to 20, wherein the catalyst has been prepared substantially as hereinbefore described in Example 1.
22. A method as claimed in Claim 1 and substantially as hereinbefore described in Example 2.
23. A mono-olefin whenever prepared by a method as claimed in any one of the preceding claims.
24. A method of preparing a chromina-alumina catalyst for use in the dehydrogenation of C3-C5 hydrocarbons for the production of mono-olefins, which method comprises spraying the alumina carrier with a solution of a soluble chromium compound to incipient wetness, followed by drying and heat treating.
25. A method as claimed in Claim 24, wherein said solution of soluble chromium compound is sprayed in an amount needed to fill 75% to 105% of the pore volume of the alumina carrier.
26. A method as claimed in Claim 25, wherein said solution is sprayed in an amount needed to fill about 90% of the pore volume of the alumina carrier.
27. A method as claimed in any one of Claims 24 to 26, wherein said soluble chromium compound is sprayed in an amount required to deposit 15 to 25% Cr203 in said carrier.
28. A method as claimed in Claim 27, wherein said soluble chromium compound is sprayed in an amount required to deposit 1719% Cr203 in said carrier.
29. A method as claimed in any one of Claims 24 to 28, wherein the said solution contains up to 0.5 wt% alkali.
30. A method as claimed in any one of Claims 24 to 29, wherein the spray impregnation is carried out at 10 to 90"C.
31. A method as claimed in Claim 30, wherein the spray impregnation is carried out at room temperature.
32. A method as claimed in any one of Claims 24 to 31, wherein the spray impregnation is carried out in 2 to 15 minutes.
33. A method as claimed in Claim 32, wherein the spray impregnation is carried out in about 5 minutes.
34. A method as claimed in any one of Claims 24 to 33, wherein said drying is at 100 to 1 800C (21 2--350"F).
35. A method as claimed in Claim 34, wherein said drying is at about 120"C (250 F) for about 2 hours.
36. A method as claimed in any one of Claims 24 to 35, wherein said heat treatment is at 650 to 800"C (1200--1470"F) for 2 to 6 hours.
37. A method as claimed in Claim 36, wherein said heat treatment is at about 760"C (1400 F) for 4 hours.
38. A method as claimed in any one of Claims 24 to 37, wherein said carrier consists essentially of eta alumina.
39. A method as claimed in Claim 24, and substantially as hereinbefore described in Example 1.
40. A chromia-alumina catalyst whenever prepared by a method as claimed in any one of Claims 24 to 39.
GB08518705A 1984-07-25 1985-07-24 Improved catalyst for hydrocarbon dehydrogenation Expired GB2162082B (en)

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US5406014A (en) * 1993-01-04 1995-04-11 Chevron Research And Technology Company Dehydrogenation processes, equipment and catalyst loads therefor
LT3553B (en) 1993-08-06 1995-12-27 Snam Progetti Process for preparing light olefins by dehydrogenation of the corresponding paraffins
LT3678B (en) 1993-09-10 1996-01-25 Snam Progetti Process for activating catalyst precursors for the dehydrogenation of c2-c5 paraffins and a catalytic composition activated by the process
FR2748021A1 (en) * 1996-04-25 1997-10-31 Atochem Elf Sa Oxidative dehydrogenation of paraffinic hydrocarbon(s) to mono-olefin(s)
US5863418A (en) * 1991-03-08 1999-01-26 Chevron Chemical Company Low-sulfur reforming process
EP0894781A1 (en) * 1997-07-29 1999-02-03 SNAMPROGETTI S.p.A. Process for obtaining light olefins by the dehydrogenation of the corresponding paraffins
WO2001023085A1 (en) * 1999-09-28 2001-04-05 Zakrytoe Aktsionernoe Obschestvo 'katalizatornaya Kompaniya' Catalyst for hydrocarbon dehydrogenation and method therefor
US7491860B2 (en) 2005-08-03 2009-02-17 Süd-Chemie Inc. Dehydrogenation process
WO2015000843A1 (en) 2013-07-02 2015-01-08 Saudi Basic Industries Corporation Process for the production of light olefins and aromatics from a hydrocarbon feedstock.
WO2015000847A1 (en) 2013-07-02 2015-01-08 Saudi Basic Industries Corporation Process and installation for the conversion of crude oil to petrochemicals having an improved propylene yield
WO2015000841A1 (en) 2013-07-02 2015-01-08 Saudi Basic Industries Corporation Process for upgrading refinery heavy residues to petrochemicals
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WO2015128046A1 (en) 2014-02-25 2015-09-03 Saudi Basic Industries Corporation An integrated hydrocracking process
US9181149B2 (en) 2007-08-03 2015-11-10 Thyssenkrupp Industrial Solutions Ag Regeneration of catalysts for dehydrating alkanes
WO2015197733A1 (en) 2014-06-26 2015-12-30 Sabic Global Technologies B.V. Process for producing alkylated aromatic hydrocarbons from a mixed hydrocarbon feedstream
US9850438B2 (en) 2014-02-25 2017-12-26 Sabic Global Technologies B.V. Integrated hydrocracking process
US9856425B2 (en) 2013-07-02 2018-01-02 Saudi Basic Industries Corporation Method of producing aromatics and light olefins from a hydrocarbon feedstock
US9856424B2 (en) 2014-02-25 2018-01-02 Saudi Basic Industries Corporation Integrated hydrocracking process
US10000708B2 (en) 2014-02-25 2018-06-19 Saudi Basic Industries Corporation Method for heating crude
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US10301561B2 (en) 2014-02-25 2019-05-28 Saudi Basic Industries Corporation Process for converting hydrocarbons into olefins
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US10479948B2 (en) 2013-07-02 2019-11-19 Saudi Basic Industries Corporation Process for the production of light olefins and aromatics from a hydrocarbon feedstock
US10717688B2 (en) 2014-06-26 2020-07-21 Sabic Global Technologies B.V. Process for producing purified aromatic hydrocarbons from a mixed hydrocarbon feedstream
US11406965B2 (en) 2016-09-07 2022-08-09 Mexichem Fluor S.A. De C.V. Catalyst and process using the catalyst for manufacturing fluorinated hydrocarbons
US11452990B2 (en) 2016-09-07 2022-09-27 Mexichem Fluor S.A. De C.V. Catalyst and process using the catalyst for manufacturing fluorinated hydrocarbons

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SA94150056B1 (en) 1993-01-04 2005-10-15 شيفرون ريسيرتش أند تكنولوجي كمبني hydrodealkylation
US5575902A (en) 1994-01-04 1996-11-19 Chevron Chemical Company Cracking processes
US6274113B1 (en) 1994-01-04 2001-08-14 Chevron Phillips Chemical Company Lp Increasing production in hydrocarbon conversion processes
US6258256B1 (en) 1994-01-04 2001-07-10 Chevron Phillips Chemical Company Lp Cracking processes
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KR20150045682A (en) * 2013-10-21 2015-04-29 한국화학연구원 Method for manufacturing olefin using continuous reaction-regeneration and fluidized mode

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US5863418A (en) * 1991-03-08 1999-01-26 Chevron Chemical Company Low-sulfur reforming process
US5406014A (en) * 1993-01-04 1995-04-11 Chevron Research And Technology Company Dehydrogenation processes, equipment and catalyst loads therefor
LT3553B (en) 1993-08-06 1995-12-27 Snam Progetti Process for preparing light olefins by dehydrogenation of the corresponding paraffins
LT3678B (en) 1993-09-10 1996-01-25 Snam Progetti Process for activating catalyst precursors for the dehydrogenation of c2-c5 paraffins and a catalytic composition activated by the process
FR2748021A1 (en) * 1996-04-25 1997-10-31 Atochem Elf Sa Oxidative dehydrogenation of paraffinic hydrocarbon(s) to mono-olefin(s)
EP0894781A1 (en) * 1997-07-29 1999-02-03 SNAMPROGETTI S.p.A. Process for obtaining light olefins by the dehydrogenation of the corresponding paraffins
US6362385B1 (en) 1997-07-29 2002-03-26 Oao Nil Yarsintez Process for obtaining light olefins by the dehydrogenation of the corresponding paraffins
WO2001023085A1 (en) * 1999-09-28 2001-04-05 Zakrytoe Aktsionernoe Obschestvo 'katalizatornaya Kompaniya' Catalyst for hydrocarbon dehydrogenation and method therefor
US7491860B2 (en) 2005-08-03 2009-02-17 Süd-Chemie Inc. Dehydrogenation process
US9181149B2 (en) 2007-08-03 2015-11-10 Thyssenkrupp Industrial Solutions Ag Regeneration of catalysts for dehydrating alkanes
US10479948B2 (en) 2013-07-02 2019-11-19 Saudi Basic Industries Corporation Process for the production of light olefins and aromatics from a hydrocarbon feedstock
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FI852865L (en) 1986-01-26
GB8518705D0 (en) 1985-08-29
DE3526533A1 (en) 1986-02-20
BR8503571A (en) 1986-04-29
NO852952L (en) 1986-01-27
GB2162082B (en) 1988-05-05

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