CA1063055A - Desulfurization of petroleum hydrocarbons - Google Patents
Desulfurization of petroleum hydrocarbonsInfo
- Publication number
- CA1063055A CA1063055A CA253,936A CA253936A CA1063055A CA 1063055 A CA1063055 A CA 1063055A CA 253936 A CA253936 A CA 253936A CA 1063055 A CA1063055 A CA 1063055A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- calculated
- cobalt
- catalyst
- molybdenum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
Abstract
ABSTRACT OF THE DISCLOSURE
Improved results in reducing the sulfur content of sulfur-containing petroleum hydrocarbons are obtained by sub-jecting selected hydrocarbon fractions containing sulfur to low pressure hydrogenation in contact with a cobalt-molybdenum-phosphorus, nickel-molybdenum-phosphorus, or cobalt-nickel-molybdenum-phosphorus catalysts under specified conditions.
Improved results in reducing the sulfur content of sulfur-containing petroleum hydrocarbons are obtained by sub-jecting selected hydrocarbon fractions containing sulfur to low pressure hydrogenation in contact with a cobalt-molybdenum-phosphorus, nickel-molybdenum-phosphorus, or cobalt-nickel-molybdenum-phosphorus catalysts under specified conditions.
Description
1063~SS
This invention relates t~ a new process for desulfur-izing petroleum hydrocarbons.
It is known in the art that the sulfur content of sulfur-containing petroleum hydrocarbons can be reduced by sub~ecting such hydrocarbons to hydr~genation in contact with a catalyst. Among the catalysts which are effective for this purpose are those which have been prepared from comp~unds of metals of Group VI of the Periodic Table in combination with compounds of metals of Group VIII of the Periodic Table. The metals are normally dispersed on a carrler such as alumina or silica-alumina. One method of impregnating these carrlers is taught in U.S. Patent 3,232,887 and involves using phosphoric acid stabilized solutions of the above-mentioned metals.
In the use of such catalysts for reducing the sulfur content of petroleum hydrocarbon fractions containing sulfur, the process is usually carried out under relatively high pres-sures. The higher pressures required in extant processes im-pose economic penalties. For example, hlgher pressure opera-tion requires expensive, thick-walled vessels and increased costs ~or higher pressure gas compressors. Furthermore, there are greater hydrogen logses at high pressure due to unrecover-able solution l!osses ln product llquid and due to chemical con-sumptlon ln reactions unessentlal to hydrodesulfurlzatlon.
To reduce hydrogen usage, a desulnurlzatlon process is needed in which slgnlflcant desulfurlzation of petroleum frac~ions is accompllshed with a minimum o~ hydrogen presssure.
~; Thé inventlon provides a -process of reducing the sul-~` fur content of sulfur-contalning petroleum hydrocarbons which oomprise~ subJectlng petroleum hydrocarbon fraction containing ~ulfur to low pre~sure hydrogenation in contact with hydrogen and a metal-molybdenum-phosphorus catalyst on a carrier wherein - ~ -1-.. , : ., -, .. . . . . . .
.. :, . . . .
the metal is from the group consisting of cobalt, nickel and mixtures of cob~lt and nickel, the amount of sald metal present in the catalyst being between 2-7% by weight calcùlated as the - metal oxide expressed as (M0), 8-20% by weight molybdenum, calculated as MoO3 and 2-10~ by weight phosphorus, calculated as P205, under the following conditions:
B R. F. Max LHSV _ (A) up to 450500_700 50 up to 10 150 (B) 450 to 650600-750 200 up to 7 500 (C) 650 to 1100 600-800 400 ùp to 4 500 (D) over 1,100650-800 400 up to 2 500 wherein B.R. represents the boiling range of the petro~leum fraction, T is the hydrogenation temperature, Max. psig. i8 the maximum hydrogen pressure in pounds per square inch gauge, LHSV is the liqùid hourly space velocity and Min. SCF/B is the minimum number of standard cubic ~eet Or hydrogen per ~2 gal-lon barrel of said petroleum fraction and separating from said contacting step said rraction having a reduced sulrur content.
The petroleum rractions containing sulrur to which the process of the invention is particularly applicable are the naphtha fraction having a boiling range up to 450F., usually in the range Or ?oo-450F.~ th~ middle distillate frac-tion having a boiling range o~ 450-650F., the heavy gas oil or vacuum gas oil rraction having a boiling range of 650-1100F., and the reslduum fraction having a boiling range from 1000F. upward. These rr ctions correspond to (A), (B), (C) and ~D), respectively, in`the foregoing statement Or the in-vention.
The catalysts which are employed ln the practice Or , ~ the invention are cobalt-molybdenum-phosphorus catalyst~, ~`
,~ , , : : ,; , , , : .
10~i30S5 nickel-molybdenum-phosphorus catalysts or catalysts prepared from a mixture D~ these metals, which can be prepared ~s de-scribed in U.S. 3,232,887, and which preferably contain the catalytic elements impregnated on a carrier. These catalysts should contain cobalt equivalent to 0.5-5% by weight CoO, molybdenum equivalent to 8-20% MoO3, pre~erably 12.5-19% by weight MoO3 ~nd phosphorus equivalent to 2-10% by weight P205, pre~erably 2.5-7% by weight P205. A preferred catalyst contains cobalt equivalent to 3% by weight CoO, molybdenum equivalent to 13% by weight MoO3, and phosphorus equivalent to 3.25% by weight P205. The nickel-molybdenum-phosphoru~ catalysts and the m~xed catalyst of cobalt-nickel-molybdenum-phosphorus may be obtained by substitutln~ickel, being calculated equiva-B lent to NiO, for cobalt ~ in the above descriptions, eitherin whole or in p~rt.
The catalyst carriers can be any of the carriers disclosed in U~S. 3,232,887 and the catalyst-carrier composite may be in any suitable physical shape, for example, rod-like or spherical. Alumina and mixtures of alumina and silica are prererred carriers. Boehmitic alumina and gamma alumlna are preferred types of carrlers.
The amount Or sulfur ln the petroleum fractlon to be treated will vary with different petroleum fractlons but wlll usually not exceed 5% by weight. Thus, ln the heavier rrac-tion3 the amount Or sulfur might be around 1.5 to 4% by weight while in lighter fractions it might be around 1% by weight.
From a practlcal standpolnt, lt 18 usually deslrable to reduce the sulrur content to not more than 0.3~ by weight. It is a ~eature of thls inventlon that processes using catalyst ob-talned rrom mlxtures of Group VI and VIII of the PerlodicTable supported on carrler~ and promoted by phosphorus unex-. :
.. , ~ . . . : , . : -- .: -. . : .- , ., - . - , 10~;305S
pectedly have been found to produce much superior desul~uriza-tion performance at lower pressures than similar processes us-ing catalysts of prior art without phosphorus while maintain-ing catalyst activity for extended periods of time.
The invention will be illustrated but is not limited by the following examples in which the quantities are stated in parts by weight unless otherwise indicated.
EXAMPLE I
An aqueous ~olution containing cobalt, molybdenum and phosphDrus was prepared as ~ollows: CoC03 (122 gms.) was slurried in one liter of water. Concentrated 85~ H3P04 (67 ml.) was added slowly with constant agitation. MoO3 (306 gms.) was added and the reactants were heated to 190;F. This temperature was held ~or 4 hours with constant stirring. The resulting clear red solution was cooled to room temperature and the vol-ume ad~usted to 1055 ml. to give a final concentration equiva-lent to 290 gms/liter in MoO3.
The cobalt-molybdenum-phosphorus containing solution was mixed well,with 25.6 pounds of dewatered boehmitic alumlna gel (14~ A1203) and one gallon o~ water. The resulting slurry was spray dried at 215 to 225F. The spray dried sample was mulled with water to give a crumbly mass of 58% ~ree moisture.
The paste was extruded into 5/64" pills, dried at 300F. and calcined at 1050F. to give a nominal 1/16" extrudate.
The resulting catalyst contained the equivalent o~
14.6% MoO3, 3.7~ CoO, and 3.1~ P205. The surface area was 362 m /gm. The pore volume was determined by nitrogen as 0.70 cm3/~m. The apparent bulk density (ABD) was 0.58 gms./ml.
EXAMPLE II
A catalyst was made from boehmitic alumina as in Example I where the alumina was lmpregnated only with moiyb-, denum oxide and cobalt carbonateO No phosphoric acid was used.
The resulting catalyst c~ntained the equivalent of 14.4% MoO3 and 3.4~ CoO. The surface area was 320 m2/gm. and the pore volume was 0.491 cm3/gm.
EXAKPLE III
This catalyst was prepared using the technlque of pore volume impregnation of a formed gamma alumina.
454 Gms. of MoO3 was slurried in 1.3 liters of water an~ 100 ml. of H3P04 was added. This slurry was then heated to 185F. and held at 185F. with stirring for one hour. After this period, 185 grams of CoC03 was slowly added to the H3P04 and MoO3 slurry. This mixture was then held at 185F. with stirring for an additional two hours and a clear solutlon was obtained. The total volume of the solutiDn after it had been allowed to cool to 90F. was 1890 ml. Th1s solution contalned the equivalent o~ 240 gms. MoO3/liter Or solution, 56.7 gms.
CoO/liter of s~lution and 56 gms. P205/liter o~ solution.
The gamma alumina used in the preparation was pre-pared by conventional means and w4s a sample of a commercially-produced alumina containing silica. The size Dr the extrudatewas 1/16" and it had an inclpient wetness pore volume Or o.85 ml./gm.
The above solution was diluted and pore volume impreg-nated onto the alumina to give a catalyst which, when analyzed, - contained the equivalent of 12.3% MoO3, 2.9% CoO, and 2.5%
This cataly~t had a surrace arèa of 240 m2/gm, and had a pore volume Or 0.55 cm3/gm.
~ IV -:
30 This catalyst was a commercial cobalt-molybdenum on alumina catalyst. The gamma alumina was prepared in the same 5_ . .
, ~ . .
, 1063~55 manner as that o~ Example III. The catalyst can be prepared by dlpping 227 gm of the calcined alumina pills in a solution containing the equivalent of 50 gm/liter of MoO3 and 21 gm/liter of CoO. The solution is prepared by dlssolving the appropriate amounts o~ ammonium heptamolybdate and cobalt nitrate in water.
The catalyst used in the ~ollowing examples contained the equivalent o~ 11.0% M~03 and 3.8% CoO. The ~ur~ace area was B 3 m /gm and the pore volume was o.s6~ cm3/gm.
The activity Df the catalysts reported in the Examples were measured using standard hydrodesulfurie~tion test pro-cedures, equipment and feedstocks. Equal volumes of catalysts were used in each case.
Results are expressed as a ratio of desul~urlz~tion rate constants multiplied by 100, K = kte t/kr fe e x 100 to ~ -give a percentage compari8on- The kreferenCe ln each ca8e ~or the non-phosphoru~ ~ntaining catalyst.
EXAMPLE_V
Te~ts were made to compare a commercial cobalt-molybdenum-phosphorus catalyst prepared in a manner slmilar to Example III with a catalyst containing substantially the same amounts of cobalt and molybdenum without the p~osphorus, i.e., the catalyst o~ Example IV, in the desulfurization o~ a 19.5API gas oil which contained 3% sulfur by weight using a ; temperature Or 675F., an LHSV of 3.5, and a hydrcgen input of 25pO SCF/B as 100% hydrogen, and at various pressures.
The results are presented in graphic form ln Figure } where përcent relatlve activity is plotted versus reactor ,. . . . . .
pres~sure. The re~erence catalyst is taken as 100%. It will be noted that maximum re~ative activity is at approximately 350 p~lg hydrogen pressure.
:
- i ,.. . .
., . ~. . . . .
161 63~55 EXAMPLE VI
In order to demonstrate the activity ~tability over a period of time, a long-term hydrodesulfurization te~t was carried out using the phosphorus-containing catalyst described in Example ~. The run condition8 were a reactor temperature of 669F., oil flow rate of 1 LHSV, a 2500 SCF/~ hydrogen to oil ratio and a pressure of 400 psig. These conditions gave an initial 89% desulfurization. The vacuum gas oil feedstock characterlstics were 2.8% sulfur, 20.0 API gravity and a boil-lng range of 742-1065F.
The resultæ are presented in Figure 2 where the tem-perature to produce a constant percentage desulfurization has been calculated and plotted versus hours on stream. This method of data presentation is chosen because in commercial reactors temperature is the vsriable usually used in control-ling the reactor to constant desulfurizatlon c~nditions. The activlty expressed in terms of temperature required to maintain a given desulfurization level was essentially constant over a period of at least 1900 hours.
EXA~P_LE VII
A mid-western diesel oil having a gravity Or 32.4API, a boiling range of 400-670F. and containing 1.27% by weight sulfur was processed to reduce the sulfur content using the same cat~lysts described in Example V at a hydrogenation tem-perature of 650F. with a hydrogen input of 1500 SCF/B and an LHSV of 3Ø Pressures over a range of 100 to 400 psig. were studied. The results are presented graphically in Figure 3 where percent relative activity i9 plotted versus reactor pres-sure. The reference, the non-phosphorus containing catalyst>
is taken as 100~ at each point.
It wlll be noted that the phosphorus-containlng .
- , , - - : :
. - : !
:lC163~355 catalyst had a higher relative activity, particularly in hydro-gen pressure ranges of 100 to 200 psig.
EXA~PLE VIII
A solution was prepared as follows: 54.7 gms. of nickel nitrate hydrate was added to 30 mls. of water along with 15.1 mls. of 85~ phosphoric acid. This solution was added to 194 mls. o~ an ammonium heptamolybdate solution con-taining the equivalent o~ 360 gm. MoO3/liter. The volume was ad~usted to 275 mls. with water. This solution was pore volume impregnated on 398.5 gms. of 1/16" gamma alumina ex-trudate similar to that used in Example III.
After calcination, the catalyst c~ntained~the equiva-lent of 14.9% MoO3, 2.97% NiO and 2.87~ P205. The sur~ace area was 255 m2/gm and the pore volume was 0.54 cm3/gm.
The resultant catalyst gives superior results when compared with a similar non-pho~phorus containing catalyst under low pressure hydrogenation conditions herein described.
; In practicing the invention, generally speaking, the lower limit of the LHSV is determined by practical considera-tions. Usually in desulfuri~ing naphtha, the LHSV will be within the range of 1-10; ln desul~urizing a middle distillate the LHSV will be within the range of 2-7; in desulfurizing heavy gas oil the LHSV will be within the range of 0.25-4. In desulfurizing residua the LHSV will be within the range of 0.25-~ 2. The lower the LHSV the greater the amount of sulfur that ; can be removed ~rom the oil. Depending on the nature o~ the feedstock, tne pr~cess càn be carried out in vapor phase or mixed liquid an~ vapor pha~e or in liquid phase. In general, the heavier the feedstock, the higher the temperature.
While the process can be carried out with pure hy-drogen, it is usually carried out with a hydrogen-containing .
.
. : , . .
1~63~)55 mixture in which the hydrogen occurs as a by-product Df other operations.
It has further been found that a particularly useful group of catalysts for desulfurizing a variety of feedstocks of the type previously described is afforded wherein the catalyst contains from 3.0-7.0% by weight of a mixture of nickel oxide and cobalt oxide, calculated as NiO and CoO; 12.0-20.0% by weight of molybdenum, calculated as MoO3 and 2.5-7.0% by weight of phosphorus, calculated as P205.
The invention is particularly useful in making it possible to desulfurize or reduce the sulfur content of various types of oils at lower pressures and with a lower hydrogen -~
input.
~" ' . ~ :
.
_g_ , , ' : .. , . :
This invention relates t~ a new process for desulfur-izing petroleum hydrocarbons.
It is known in the art that the sulfur content of sulfur-containing petroleum hydrocarbons can be reduced by sub~ecting such hydrocarbons to hydr~genation in contact with a catalyst. Among the catalysts which are effective for this purpose are those which have been prepared from comp~unds of metals of Group VI of the Periodic Table in combination with compounds of metals of Group VIII of the Periodic Table. The metals are normally dispersed on a carrler such as alumina or silica-alumina. One method of impregnating these carrlers is taught in U.S. Patent 3,232,887 and involves using phosphoric acid stabilized solutions of the above-mentioned metals.
In the use of such catalysts for reducing the sulfur content of petroleum hydrocarbon fractions containing sulfur, the process is usually carried out under relatively high pres-sures. The higher pressures required in extant processes im-pose economic penalties. For example, hlgher pressure opera-tion requires expensive, thick-walled vessels and increased costs ~or higher pressure gas compressors. Furthermore, there are greater hydrogen logses at high pressure due to unrecover-able solution l!osses ln product llquid and due to chemical con-sumptlon ln reactions unessentlal to hydrodesulfurlzatlon.
To reduce hydrogen usage, a desulnurlzatlon process is needed in which slgnlflcant desulfurlzation of petroleum frac~ions is accompllshed with a minimum o~ hydrogen presssure.
~; Thé inventlon provides a -process of reducing the sul-~` fur content of sulfur-contalning petroleum hydrocarbons which oomprise~ subJectlng petroleum hydrocarbon fraction containing ~ulfur to low pre~sure hydrogenation in contact with hydrogen and a metal-molybdenum-phosphorus catalyst on a carrier wherein - ~ -1-.. , : ., -, .. . . . . . .
.. :, . . . .
the metal is from the group consisting of cobalt, nickel and mixtures of cob~lt and nickel, the amount of sald metal present in the catalyst being between 2-7% by weight calcùlated as the - metal oxide expressed as (M0), 8-20% by weight molybdenum, calculated as MoO3 and 2-10~ by weight phosphorus, calculated as P205, under the following conditions:
B R. F. Max LHSV _ (A) up to 450500_700 50 up to 10 150 (B) 450 to 650600-750 200 up to 7 500 (C) 650 to 1100 600-800 400 ùp to 4 500 (D) over 1,100650-800 400 up to 2 500 wherein B.R. represents the boiling range of the petro~leum fraction, T is the hydrogenation temperature, Max. psig. i8 the maximum hydrogen pressure in pounds per square inch gauge, LHSV is the liqùid hourly space velocity and Min. SCF/B is the minimum number of standard cubic ~eet Or hydrogen per ~2 gal-lon barrel of said petroleum fraction and separating from said contacting step said rraction having a reduced sulrur content.
The petroleum rractions containing sulrur to which the process of the invention is particularly applicable are the naphtha fraction having a boiling range up to 450F., usually in the range Or ?oo-450F.~ th~ middle distillate frac-tion having a boiling range o~ 450-650F., the heavy gas oil or vacuum gas oil rraction having a boiling range of 650-1100F., and the reslduum fraction having a boiling range from 1000F. upward. These rr ctions correspond to (A), (B), (C) and ~D), respectively, in`the foregoing statement Or the in-vention.
The catalysts which are employed ln the practice Or , ~ the invention are cobalt-molybdenum-phosphorus catalyst~, ~`
,~ , , : : ,; , , , : .
10~i30S5 nickel-molybdenum-phosphorus catalysts or catalysts prepared from a mixture D~ these metals, which can be prepared ~s de-scribed in U.S. 3,232,887, and which preferably contain the catalytic elements impregnated on a carrier. These catalysts should contain cobalt equivalent to 0.5-5% by weight CoO, molybdenum equivalent to 8-20% MoO3, pre~erably 12.5-19% by weight MoO3 ~nd phosphorus equivalent to 2-10% by weight P205, pre~erably 2.5-7% by weight P205. A preferred catalyst contains cobalt equivalent to 3% by weight CoO, molybdenum equivalent to 13% by weight MoO3, and phosphorus equivalent to 3.25% by weight P205. The nickel-molybdenum-phosphoru~ catalysts and the m~xed catalyst of cobalt-nickel-molybdenum-phosphorus may be obtained by substitutln~ickel, being calculated equiva-B lent to NiO, for cobalt ~ in the above descriptions, eitherin whole or in p~rt.
The catalyst carriers can be any of the carriers disclosed in U~S. 3,232,887 and the catalyst-carrier composite may be in any suitable physical shape, for example, rod-like or spherical. Alumina and mixtures of alumina and silica are prererred carriers. Boehmitic alumina and gamma alumlna are preferred types of carrlers.
The amount Or sulfur ln the petroleum fractlon to be treated will vary with different petroleum fractlons but wlll usually not exceed 5% by weight. Thus, ln the heavier rrac-tion3 the amount Or sulfur might be around 1.5 to 4% by weight while in lighter fractions it might be around 1% by weight.
From a practlcal standpolnt, lt 18 usually deslrable to reduce the sulrur content to not more than 0.3~ by weight. It is a ~eature of thls inventlon that processes using catalyst ob-talned rrom mlxtures of Group VI and VIII of the PerlodicTable supported on carrler~ and promoted by phosphorus unex-. :
.. , ~ . . . : , . : -- .: -. . : .- , ., - . - , 10~;305S
pectedly have been found to produce much superior desul~uriza-tion performance at lower pressures than similar processes us-ing catalysts of prior art without phosphorus while maintain-ing catalyst activity for extended periods of time.
The invention will be illustrated but is not limited by the following examples in which the quantities are stated in parts by weight unless otherwise indicated.
EXAMPLE I
An aqueous ~olution containing cobalt, molybdenum and phosphDrus was prepared as ~ollows: CoC03 (122 gms.) was slurried in one liter of water. Concentrated 85~ H3P04 (67 ml.) was added slowly with constant agitation. MoO3 (306 gms.) was added and the reactants were heated to 190;F. This temperature was held ~or 4 hours with constant stirring. The resulting clear red solution was cooled to room temperature and the vol-ume ad~usted to 1055 ml. to give a final concentration equiva-lent to 290 gms/liter in MoO3.
The cobalt-molybdenum-phosphorus containing solution was mixed well,with 25.6 pounds of dewatered boehmitic alumlna gel (14~ A1203) and one gallon o~ water. The resulting slurry was spray dried at 215 to 225F. The spray dried sample was mulled with water to give a crumbly mass of 58% ~ree moisture.
The paste was extruded into 5/64" pills, dried at 300F. and calcined at 1050F. to give a nominal 1/16" extrudate.
The resulting catalyst contained the equivalent o~
14.6% MoO3, 3.7~ CoO, and 3.1~ P205. The surface area was 362 m /gm. The pore volume was determined by nitrogen as 0.70 cm3/~m. The apparent bulk density (ABD) was 0.58 gms./ml.
EXAMPLE II
A catalyst was made from boehmitic alumina as in Example I where the alumina was lmpregnated only with moiyb-, denum oxide and cobalt carbonateO No phosphoric acid was used.
The resulting catalyst c~ntained the equivalent of 14.4% MoO3 and 3.4~ CoO. The surface area was 320 m2/gm. and the pore volume was 0.491 cm3/gm.
EXAKPLE III
This catalyst was prepared using the technlque of pore volume impregnation of a formed gamma alumina.
454 Gms. of MoO3 was slurried in 1.3 liters of water an~ 100 ml. of H3P04 was added. This slurry was then heated to 185F. and held at 185F. with stirring for one hour. After this period, 185 grams of CoC03 was slowly added to the H3P04 and MoO3 slurry. This mixture was then held at 185F. with stirring for an additional two hours and a clear solutlon was obtained. The total volume of the solutiDn after it had been allowed to cool to 90F. was 1890 ml. Th1s solution contalned the equivalent o~ 240 gms. MoO3/liter Or solution, 56.7 gms.
CoO/liter of s~lution and 56 gms. P205/liter o~ solution.
The gamma alumina used in the preparation was pre-pared by conventional means and w4s a sample of a commercially-produced alumina containing silica. The size Dr the extrudatewas 1/16" and it had an inclpient wetness pore volume Or o.85 ml./gm.
The above solution was diluted and pore volume impreg-nated onto the alumina to give a catalyst which, when analyzed, - contained the equivalent of 12.3% MoO3, 2.9% CoO, and 2.5%
This cataly~t had a surrace arèa of 240 m2/gm, and had a pore volume Or 0.55 cm3/gm.
~ IV -:
30 This catalyst was a commercial cobalt-molybdenum on alumina catalyst. The gamma alumina was prepared in the same 5_ . .
, ~ . .
, 1063~55 manner as that o~ Example III. The catalyst can be prepared by dlpping 227 gm of the calcined alumina pills in a solution containing the equivalent of 50 gm/liter of MoO3 and 21 gm/liter of CoO. The solution is prepared by dlssolving the appropriate amounts o~ ammonium heptamolybdate and cobalt nitrate in water.
The catalyst used in the ~ollowing examples contained the equivalent o~ 11.0% M~03 and 3.8% CoO. The ~ur~ace area was B 3 m /gm and the pore volume was o.s6~ cm3/gm.
The activity Df the catalysts reported in the Examples were measured using standard hydrodesulfurie~tion test pro-cedures, equipment and feedstocks. Equal volumes of catalysts were used in each case.
Results are expressed as a ratio of desul~urlz~tion rate constants multiplied by 100, K = kte t/kr fe e x 100 to ~ -give a percentage compari8on- The kreferenCe ln each ca8e ~or the non-phosphoru~ ~ntaining catalyst.
EXAMPLE_V
Te~ts were made to compare a commercial cobalt-molybdenum-phosphorus catalyst prepared in a manner slmilar to Example III with a catalyst containing substantially the same amounts of cobalt and molybdenum without the p~osphorus, i.e., the catalyst o~ Example IV, in the desulfurization o~ a 19.5API gas oil which contained 3% sulfur by weight using a ; temperature Or 675F., an LHSV of 3.5, and a hydrcgen input of 25pO SCF/B as 100% hydrogen, and at various pressures.
The results are presented in graphic form ln Figure } where përcent relatlve activity is plotted versus reactor ,. . . . . .
pres~sure. The re~erence catalyst is taken as 100%. It will be noted that maximum re~ative activity is at approximately 350 p~lg hydrogen pressure.
:
- i ,.. . .
., . ~. . . . .
161 63~55 EXAMPLE VI
In order to demonstrate the activity ~tability over a period of time, a long-term hydrodesulfurization te~t was carried out using the phosphorus-containing catalyst described in Example ~. The run condition8 were a reactor temperature of 669F., oil flow rate of 1 LHSV, a 2500 SCF/~ hydrogen to oil ratio and a pressure of 400 psig. These conditions gave an initial 89% desulfurization. The vacuum gas oil feedstock characterlstics were 2.8% sulfur, 20.0 API gravity and a boil-lng range of 742-1065F.
The resultæ are presented in Figure 2 where the tem-perature to produce a constant percentage desulfurization has been calculated and plotted versus hours on stream. This method of data presentation is chosen because in commercial reactors temperature is the vsriable usually used in control-ling the reactor to constant desulfurizatlon c~nditions. The activlty expressed in terms of temperature required to maintain a given desulfurization level was essentially constant over a period of at least 1900 hours.
EXA~P_LE VII
A mid-western diesel oil having a gravity Or 32.4API, a boiling range of 400-670F. and containing 1.27% by weight sulfur was processed to reduce the sulfur content using the same cat~lysts described in Example V at a hydrogenation tem-perature of 650F. with a hydrogen input of 1500 SCF/B and an LHSV of 3Ø Pressures over a range of 100 to 400 psig. were studied. The results are presented graphically in Figure 3 where percent relative activity i9 plotted versus reactor pres-sure. The reference, the non-phosphorus containing catalyst>
is taken as 100~ at each point.
It wlll be noted that the phosphorus-containlng .
- , , - - : :
. - : !
:lC163~355 catalyst had a higher relative activity, particularly in hydro-gen pressure ranges of 100 to 200 psig.
EXA~PLE VIII
A solution was prepared as follows: 54.7 gms. of nickel nitrate hydrate was added to 30 mls. of water along with 15.1 mls. of 85~ phosphoric acid. This solution was added to 194 mls. o~ an ammonium heptamolybdate solution con-taining the equivalent o~ 360 gm. MoO3/liter. The volume was ad~usted to 275 mls. with water. This solution was pore volume impregnated on 398.5 gms. of 1/16" gamma alumina ex-trudate similar to that used in Example III.
After calcination, the catalyst c~ntained~the equiva-lent of 14.9% MoO3, 2.97% NiO and 2.87~ P205. The sur~ace area was 255 m2/gm and the pore volume was 0.54 cm3/gm.
The resultant catalyst gives superior results when compared with a similar non-pho~phorus containing catalyst under low pressure hydrogenation conditions herein described.
; In practicing the invention, generally speaking, the lower limit of the LHSV is determined by practical considera-tions. Usually in desulfuri~ing naphtha, the LHSV will be within the range of 1-10; ln desul~urizing a middle distillate the LHSV will be within the range of 2-7; in desulfurizing heavy gas oil the LHSV will be within the range of 0.25-4. In desulfurizing residua the LHSV will be within the range of 0.25-~ 2. The lower the LHSV the greater the amount of sulfur that ; can be removed ~rom the oil. Depending on the nature o~ the feedstock, tne pr~cess càn be carried out in vapor phase or mixed liquid an~ vapor pha~e or in liquid phase. In general, the heavier the feedstock, the higher the temperature.
While the process can be carried out with pure hy-drogen, it is usually carried out with a hydrogen-containing .
.
. : , . .
1~63~)55 mixture in which the hydrogen occurs as a by-product Df other operations.
It has further been found that a particularly useful group of catalysts for desulfurizing a variety of feedstocks of the type previously described is afforded wherein the catalyst contains from 3.0-7.0% by weight of a mixture of nickel oxide and cobalt oxide, calculated as NiO and CoO; 12.0-20.0% by weight of molybdenum, calculated as MoO3 and 2.5-7.0% by weight of phosphorus, calculated as P205.
The invention is particularly useful in making it possible to desulfurize or reduce the sulfur content of various types of oils at lower pressures and with a lower hydrogen -~
input.
~" ' . ~ :
.
_g_ , , ' : .. , . :
Claims (8)
1. A process of reducing the sulfur content of sul-fur-containing petroleum hydrocarbons which comprises subject-ing petroleum hydrocarbon fractions containing sulfur to low pressure hydrogenation in contact with hydrogen and a metal-molybdenum-phosphorus catalyst on a carrier wherein the metal is from the group consisting of cobalt, nickel and mixtures of cobalt and nickel, the amount of said metal present in the catalyst being between 2-7% by weight calculated as the metal oxide expressed as (Mb), 8-20% by weight molybdenum, calculated as MoO3 and 2-10% by weight phosphorus, calculated as P2O5, under the following conditions:
wherein B.R. represents the boiling range of the petroleum fraction, T is the hydrogenation temperature, Max. psig. is the maximum hydrogen pressure in pounds per square inch gauge, LHSV is the liquid hourly space velocity and Min. SCF/B is the minimum number of standard cubic feet of hydrogen per 42 gal-lon barrel of said petroleum fraction and separating from said contacting step said fraction having a reduced sulfur content.
wherein B.R. represents the boiling range of the petroleum fraction, T is the hydrogenation temperature, Max. psig. is the maximum hydrogen pressure in pounds per square inch gauge, LHSV is the liquid hourly space velocity and Min. SCF/B is the minimum number of standard cubic feet of hydrogen per 42 gal-lon barrel of said petroleum fraction and separating from said contacting step said fraction having a reduced sulfur content.
2. A process as claimed in claim 1 in which the metal is cobalt.
3. A process as claimed in claim 1 in which said conditions correspond to (A).
4. A process as claimed in claim 1 in which said conditions correspond to (B).
5. A process as claimed in claim 1 in which said conditions correspond to (C).
6. A process as claimed in claim 1 in which said conditions correspond to (D).
7. A process as claimed in claim 1 in which said catalyst comprises 2.5-4.0% by weight cobalt, calculated as CoO, 12.5-15.0% by weight molybdenum, calculated as MoO3 and 2.5-7.0% by weight phosphorus, calculated as P2O5.
8. A process as claimed in claim 1 in which said catalyst comprises 3.0-6.0% by weight of cobalt and nickel oxide, calculated as NiOCoO, 12.0-20.0% by weight molybdenum, calculated as MoO3 and 2.5-7.0% by weight phosphorus, calcu-lated as P2O5.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US59095875A | 1975-06-27 | 1975-06-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1063055A true CA1063055A (en) | 1979-09-25 |
Family
ID=24364435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA253,936A Expired CA1063055A (en) | 1975-06-27 | 1976-06-02 | Desulfurization of petroleum hydrocarbons |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS525807A (en) |
| CA (1) | CA1063055A (en) |
| DE (1) | DE2628531A1 (en) |
| FR (1) | FR2315533A1 (en) |
| GB (1) | GB1514671A (en) |
| IT (1) | IT1069975B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2904242B1 (en) * | 2006-07-28 | 2012-09-28 | Inst Francais Du Petrole | PROCESS FOR HYDRODESULFURING CUTS CONTAINING SULFUR COMPOUNDS AND OLEFINS IN THE PRESENCE OF A SUPPORTED CATALYST COMPRISING ELEMENTS OF GROUPS VIII AND VIB |
| WO2020083945A1 (en) | 2018-10-22 | 2020-04-30 | Total Marketing Services | Deep desulphurization of low sulphur content feedstock |
| CN109529899A (en) * | 2018-12-04 | 2019-03-29 | 宁波中科远东催化工程技术有限公司 | Heavy-oil hydrogenation composite catalyst and preparation method thereof and application method |
-
1976
- 1976-06-02 CA CA253,936A patent/CA1063055A/en not_active Expired
- 1976-06-04 GB GB2324376A patent/GB1514671A/en not_active Expired
- 1976-06-18 FR FR7618714A patent/FR2315533A1/en active Granted
- 1976-06-22 IT IT5006576A patent/IT1069975B/en active
- 1976-06-24 DE DE19762628531 patent/DE2628531A1/en active Pending
- 1976-06-25 JP JP51075404A patent/JPS525807A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5348206B2 (en) | 1978-12-27 |
| DE2628531A1 (en) | 1976-12-30 |
| JPS525807A (en) | 1977-01-17 |
| GB1514671A (en) | 1978-06-21 |
| FR2315533B1 (en) | 1981-09-11 |
| FR2315533A1 (en) | 1977-01-21 |
| IT1069975B (en) | 1985-03-25 |
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