EP0420652A1 - Procédé d'hydrotraitement en suspension - Google Patents

Procédé d'hydrotraitement en suspension Download PDF

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Publication number
EP0420652A1
EP0420652A1 EP90310611A EP90310611A EP0420652A1 EP 0420652 A1 EP0420652 A1 EP 0420652A1 EP 90310611 A EP90310611 A EP 90310611A EP 90310611 A EP90310611 A EP 90310611A EP 0420652 A1 EP0420652 A1 EP 0420652A1
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EP
European Patent Office
Prior art keywords
catalyst
hydrotreating
hydrogen
zone
heavy
Prior art date
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Application number
EP90310611A
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German (de)
English (en)
Inventor
William Edward Winter, Jr.
Willard Hall Sawyer
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Publication date
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Publication of EP0420652A1 publication Critical patent/EP0420652A1/fr
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    • 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
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/56—Hydrogenation of the aromatic hydrocarbons with moving solid particles
    • 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
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used

Definitions

  • This invention relates to the use of a catalyst slurry for hydrotreating heavy fossil fuel feedstocks such as vacuum gas oils or heavy gas oils.
  • High catalyst activity is maintained by circulating the catalyst between a hydrotreating zone and a hydrogen stripping reactivation zone.
  • the petroleum industry employs hydrotreating to process heavy vacuum gas oils, particularly coker gas oils, in order to improve their quality as fluid catalytic cracker (FCC) feeds.
  • Hydrotreating accom­plishes the saturation of multi-ring aromatic compounds to one-ring aromatics or completely saturated naphthenes. This is necessary to assure low coke and high gasoline yields in the cat cracker.
  • Multi-ring aromatics cannot be cracked effectively to mogas and heating oil products, whereas partially hydrogenated aromatics or naphthenes can be cracked to premium products.
  • Hydrotreating is further capable of removing sulfur and nitrogen which is detrimental to the crack­ing process.
  • Hydrotreating employs catalysts that tend to become poisoned by organic nitrogen compounds in the feed. Such compounds become adsorbed onto the catalyst and tie up needed hydrogenation sites due to the slow kinetics or turnover for hydrodenitrogenation. Higher temperatures may be utilized to overcome this problem. However, at high temperatures thermodynamic equilibrium tends to favor the preservation of undesirable multi-­ring aromatic compounds.
  • Patent No. 4,557,821 to Lopez et al discloses hydrotreating a heavy oil employing a circulating slurry catalyst.
  • Other patents disclosing slurry hydrotreating include U.S. Patent Nos. 3,297,563; 2,912,375; and 2,700,015.
  • the present invention is directed to a method of maintaining high catalyst activity in a slurry hydrotreating process for heavy fossil fuels wherein a hydrotreating catalyst of small particle size is contacted with heavy petroleum or synfuel stocks for hydrogenation of heavy aromatics and removal of nitro­gen and sulfur.
  • the catalyst is circulated between a hydrotreating reaction zone and hydrogen stripping reactivation zone.
  • Fig. 1 shows a schematic diagram of one process scheme according to this invention comprising a slurry hydro­treating step and hydrogen reactivation stripping step.
  • Applicants' process is directed to a slurry hydrotreating process in which the catalyst used in a hydrotreating zone is reactivated by hydrogen stripping in a cyclic, preferably continuous process.
  • the catalyst is reactivated in a separate reactivation zone and recycled back to the hydro­treating zone.
  • fresh or reactivated (regenerated) catalyst can be continually added while aged or deactivated catalyst can be purged or reacti­vated.
  • the slurry hydro­treating step can be operated at more severe conditions (which otherwise tend to deactivate the catalyst) than used in conventional fixed bed hydrotreating.
  • a conventional fixed bed hydrotreater typically operates for about 1 or 2 years before it is necessary to shut it down in order to replace the catalyst.
  • the slurry hydrotreating process of this invention can be used to treat various feeds including fossil fuels such as heavy catalytic cracking cycle oils (HCCO), coker gas oils, and vacuum gas oils (VGO) which contain significant concentrations of multi-ring and polar aromatics, particularly large asphaltenic molecules.
  • HCCO heavy catalytic cracking cycle oils
  • VGO vacuum gas oils
  • Similar gas oils derived from petroleum, coal, bitumen, tar sands, or shale oil are suitable feeds.
  • Suitable feeds for processing according to the present invention include those gas oil fractions which are distilled in the range of 500 to 1200°F, preferably in the 650 to 1100°F range. Above 1200°F it is difficult or impossible to strip all of the feed off the catalyst with hydrogen and the catalyst tends to coke up. Also, the presence of concarbon and asphaltenes deactivate the catalyst.
  • the feed should not be such that more than 10% boils above 1050°F.
  • the nitrogen content is normally greater than 1500 ppm.
  • the 3+ ring aromatics content of the feed will generally represent 25% or more by weight. Polar aromatics are generally 5% or more by weight and concarbon con­stitutes 1% or more by weight.
  • Suitable catalysts for use in the present process are well known in the art and include, but are not limited to, molybdenum (Mo) sulfides, mixtures of transition metal sulfides such as Ni, No, Co, Fe, W, Mn, and the like.
  • Mo molybdenum
  • Typical catalysts include NiMo, CoMo, or CoNiMo combinations.
  • sulfides of Group VII metals are suitable.
  • catalyst materials can be unsupported or supported on inorganic oxides such as alumina, silica, titania, silica alumina, silica magnesia and mixtures thereof.
  • Zeolites such as USY or acid micro supports such as aluminated CAB-O-SIL can be suitably composited with these supports.
  • Catalysts formed in-situ from soluble precursors such as Ni and Mo naphthenate or salts of phosphomolybdic acids are suitable.
  • the catalyst material may range in diameter from 1 ⁇ to 1/8 inch.
  • the cata­lyst particles are 1 to 400 ⁇ in diameter so that intra particle diffusion limitations are minimized or elimi­nated during hydrotreating.
  • transition metals such as Mo are suitably present at a weight percent of 5 to 30%, preferably 10 to 20%.
  • Promoter metals such as Ni and/or Co are typically present in the amount of 1 to 15%.
  • the surface area is suitably about 80 to 400 m2/g, preferably 150 to 300 m2/g.
  • the alumina support is formed by precipitating alumina in hydrous form from a mixture of acidic reagents in an alkaline aqueous aluminate solution. A slurry is formed upon precipitation of the hydrous alumina. This slurry is concentrated and generally spray dried to provide a catalyst support or carrier. The carrier is then impregnated with cataly­tic metals and subsequently calcined.
  • suitable reagents and conditions for preparing the support are disclosed in U.S. patents Nos. 3,770,617 and 3,531,398, herein incorporated by reference.
  • the well known oil drop method comprises forming an alumina hydrosol by any of the teachings taught in the prior art, for example by reacting aluminum with hydrochloric acid, combining the hydrosol with a suitable gelling agent and dropping the resultant mixture into an oil bath until hydrogel spheres are formed. The spheres are then continuously withdrawn from the oil bath, washed, dried, and calcined.
  • This treatment converts the alumina hydrogel to corresponding crystalline gamma alumina particles. They are then impregnated with catalytic metals as with spray dried particles. See for example, U.S. Patents Nos. 3,745,112 and 2,620,314.
  • the feedstream is typically mixed with a hydrogen containing gas in stream 3 and heated to a reaction temperature in a furnace or preheater 4.
  • a make-up hydrogen stream 30 may be introduced into the hydrogen stream 3, which in turn may be either com­bined with the feed stream or alternatively mixed in the hydrotreating reactor 2.
  • the hydrotreating reactor contains a catalyst in the form of a slurry at a solids weight percent of about 10 to 70 percent, preferably 40 to 60 percent.
  • the feed enters through the bottom of the reactor and bubbles up through an ebulating or fluidized bed.
  • the hydrotreating reactor may have filters at the entrance and/or exit orifices to keep the catalyst particles in the reactor.
  • the reactor may have a flare (increasing diameter) configuration such that when the reactor is kept at minimum fluidi­zation velocity, the catalyst particles are prevented from escaping through an upper exit orifice.
  • a single slurry hydrotreating reactor may be used in the present process, it is preferred for greater efficiencies that the slurry hydrotreating process be operated in two or more stages, as disclosed in copending U.S. Application No. 414,175, hereby incorporated by reference.
  • a high temperature stage may be followed by one or more low temperature stages.
  • a two stage process might process fresh feed in a 760°F stage and process the product from the first stage in a 720°F stage.
  • several stages can be operated at successively lower temperatures, such as a 780°F stage followed by a 740°F stage followed by a 700°F stage.
  • Staging is espe­cially advantageous in the present slurry process as compared to a fixed bed process because the initial stages can be operated at higher temperatures, heat transfer is better and diffusion does not limit reac­tion rates.
  • an effluent from the hydrotreating reactor 2 containing liquids and gases and substantially no catalyst solids, is passed via stream 5 through a cooler 6 and introduced into a gas-liquid separator or disengaging means 7 where the hydrogen gas along with ammonia and hydrogen sulfide by-products from the hydrotreating reactions may be separated from the liquid product in stream 8.
  • the separated gases in stream 11 are recycled via com­pressor 10 back for reuse in the hydrogen stream 3.
  • the recycled gas is usually passed through a scrubber to remove hydrogen sul fide and ammonia because of their inhibiting effects on the kinetics of hydrotreating and also to reduce corrosion in the recycle circuit.
  • the liquid product in stream 8 is given a light caustic wash to assure complete removal of hydrogen sulfide.
  • Small quantities of hydrogen sulfide, if left in the product, will oxidize to free sulfur upon exposure to the air, and may cause the product to exceed pollution or corrosion specifi­cations.
  • an exit stream containing catalyst solids is removed from the reactor as stream 12 and enters a separator 14, which may be a filter, vacuum flash, centrifuge, or the like to divide the effluent into a catalyst stream 15 and a liquid stream 16 for recycle via pump 17 to the hydrotreating reactor 2.
  • a separator 14 may be a filter, vacuum flash, centrifuge, or the like to divide the effluent into a catalyst stream 15 and a liquid stream 16 for recycle via pump 17 to the hydrotreating reactor 2.
  • the catalyst stream 15 from separator 14 comprises suitably 30 to 60 percent catalyst.
  • this catalyst stream may be diluted with a lighter liquid such as naphtha to fluidize the catalyst and aid in the transport of the catalyst, while permitting easy separation by distillation and recycle.
  • the catalyst material is transported to the stripper reactor or reactivator 20.
  • a hydrogen stream 22, preferably heated in heater 21, is introduced into reactivator 20 where the catalyst is hydrogen stripped.
  • the reactivator yields a reactivated catalyst stream 23 for recycle back to the hydrotreating reactor 2.
  • Spent catalyst may be purged from stream 23 via line 24 and fresh make-up catalyst introduced via line 18 into the feed stream.
  • the reactivated catalyst from the reactivator 20 is suitably returned to the hydro­treating reactor 2 at a rate of about 0.05 to 0.50 lbs reactivated catalyst to lbs gas oil feed, preferably 0.1 to 0.3.
  • the reactivator 20 also yields a top gas stream 25 which is subsequently passed through cooler 26, gas-liquid separator 27 and via stream 13 combined with the hydrogen recycle stream 11. Off gas may be purged via line 29. Stripped liquids from the separa­tor 27 may be returned to the hydrotreater reactor 2 via stream 28.
  • the process conditions in the process depend to some extent on the particular feed being treated.
  • the hydrotreating zone of the reactor is suitably at a temperature of about 650 to 780°F, preferably 675 to 750°F and at a pressure of 800 to 4000 psig, preferably 1500 to 2500 psig.
  • the hydrogen treat gas rate is 1500 to 10,000 SCF/B, preferably 2500 to 5000 SCF/B.
  • the space velocity or holding time (WHSV, lb/lb of cata­lyst-hr) is suitably 0.2 to 5.0, preferably 0.5 to 2.0.
  • the reactivating zone is suitably maintained at a temperature of about 650 to 780°F, preferably 675 to 750°F, and a pressure of about 800 to 4000 psig, preferably 1500 to 2500.
  • the strip rate (SCF/ lb catalyst-hr) is suitably about 0.03 to 7, preferably 0.15 to 1.5.
  • the autoclave was heated to 720°F under 1200 psig hydrogen pressure.
  • the autoclave was operated in a gas flow thru mode so that hydrogen treat gas was added continuously while gaseous products were taken off. Hydrogen was added over the course of the run so that the initial hydrogen charge plus make-up hydrogen was equivalent to 3500 SCF/B of liquid charged to the autoclave.
  • the autoclave was quenched or cooled quickly to stop reactions.
  • the autoclave reactor was de-pressured and the catalyst was filtered from the liquid products. These products were then analyzed to determine the extent of HDS (hydrodesulfurization), HDN (hydro­denitrogenation), and aromatics hydrogenation. The results are shown in Table III below.
  • Catalyst discharged from an autoclave run at the same conditions as in Experiment 1 was filtered and charged to the autoclave with the same feed as the previous runs. The same filtered catalyst was recycled in the autoclave several times in order to line out catalyst performance. The results of these runs are shown below.
  • the catalyst was filtered from the products and recycled in an autoclave run several times in order to line-out catalyst performance.
  • the results of these runs with the hydrogen stripped, aged catalyst and the filtered, aged catalyst are shown in Table IV.
  • Table IV Slurry Catalyst Loading and Product Quality Hydrogen Stripped, Aged Catalyst Recycled, Filtered, Aged Catalyst Slurry Catalyst Loading Wt% Catalyst on FF 31.5 31.5 Slurry Product Quality Wt% Sulfur 0.20 0.25 Wt% Nitrogen 0.14 0.27 Wt% Sats + 1R AR 62 56 Wt% 3+ R AR & Polars 25 29 Wt% Polar AR 3.6 5.2

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
EP90310611A 1989-09-28 1990-09-27 Procédé d'hydrotraitement en suspension Withdrawn EP0420652A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US41416689A 1989-09-28 1989-09-28
US414166 1989-09-28

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JP (1) JPH03131685A (fr)
CA (1) CA2025220A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11427782B2 (en) 2018-07-20 2022-08-30 Neste Oyj Purification of recycled and renewable organic material
US11499104B2 (en) 2018-07-20 2022-11-15 Neste Oyj Purification of recycled and renewable organic material
US11624030B2 (en) 2018-07-20 2023-04-11 Neste Oyj Production of hydrocarbons from recycled or renewable organic material
US11655422B2 (en) 2018-07-20 2023-05-23 Neste Oyj Purification of recycled and renewable organic material
US11981869B2 (en) 2018-07-20 2024-05-14 Neste Oyj Purification of recycled and renewable organic material

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100219601B1 (ko) * 1996-05-15 1999-09-01 윤종용 인쇄면 판별영역을 갖는 ohp 및 승화형 열전사 프린터의 ohp 인쇄면 판별 방법 및 이에 적합한 장치
KR101697823B1 (ko) * 2014-12-09 2017-01-19 고려대학교 산학협력단 코발트-몰리브데늄 나노 입자 및 그의 제조 방법
CN109078665B (zh) * 2018-09-05 2024-08-16 江苏德威新材料股份有限公司 恒温油浴器

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2649419A (en) * 1950-11-16 1953-08-18 Sun Oil Co Molybdenum disulfide containing hydrogenation catalyst
US3812028A (en) * 1971-05-18 1974-05-21 Standard Oil Co Hydrotreatment of fossil fuels
US4610779A (en) * 1984-10-05 1986-09-09 Exxon Research And Engineering Co. Process for the hydrogenation of aromatic hydrocarbons
DE3629631A1 (de) * 1986-08-30 1988-03-03 Basf Ag Verfahren zur herstellung von medizinischen weissoelen und medizinischen paraffinen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2649419A (en) * 1950-11-16 1953-08-18 Sun Oil Co Molybdenum disulfide containing hydrogenation catalyst
US3812028A (en) * 1971-05-18 1974-05-21 Standard Oil Co Hydrotreatment of fossil fuels
US4610779A (en) * 1984-10-05 1986-09-09 Exxon Research And Engineering Co. Process for the hydrogenation of aromatic hydrocarbons
DE3629631A1 (de) * 1986-08-30 1988-03-03 Basf Ag Verfahren zur herstellung von medizinischen weissoelen und medizinischen paraffinen

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11427782B2 (en) 2018-07-20 2022-08-30 Neste Oyj Purification of recycled and renewable organic material
EP3824053B1 (fr) * 2018-07-20 2022-08-31 Neste Oyj Purification de matière organique recyclée et renouvelable
US11499104B2 (en) 2018-07-20 2022-11-15 Neste Oyj Purification of recycled and renewable organic material
US11624030B2 (en) 2018-07-20 2023-04-11 Neste Oyj Production of hydrocarbons from recycled or renewable organic material
US11655422B2 (en) 2018-07-20 2023-05-23 Neste Oyj Purification of recycled and renewable organic material
US11981869B2 (en) 2018-07-20 2024-05-14 Neste Oyj Purification of recycled and renewable organic material

Also Published As

Publication number Publication date
CA2025220A1 (fr) 1991-03-29
JPH03131685A (ja) 1991-06-05

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