EP0554151B1 - Procédé d'hydrogénation sélective, notamment des dioléfines dans les essences de vapocraquage, avec un catalyseur sous forme de lits mis en oeuvre successivement - Google Patents

Procédé d'hydrogénation sélective, notamment des dioléfines dans les essences de vapocraquage, avec un catalyseur sous forme de lits mis en oeuvre successivement Download PDF

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Publication number
EP0554151B1
EP0554151B1 EP93400164A EP93400164A EP0554151B1 EP 0554151 B1 EP0554151 B1 EP 0554151B1 EP 93400164 A EP93400164 A EP 93400164A EP 93400164 A EP93400164 A EP 93400164A EP 0554151 B1 EP0554151 B1 EP 0554151B1
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EP
European Patent Office
Prior art keywords
bed
charge
catalyst
product
beds
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.)
Expired - Lifetime
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EP93400164A
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German (de)
English (en)
French (fr)
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EP0554151A1 (fr
Inventor
Jean Cosyns
Patrick Sarrazin
Jean-Paul Boitiaux
Charles Cameron
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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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
    • 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
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/06—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a selective hydrogenation of the diolefins

Definitions

  • the present invention relates to a hydrogenation process and more particularly to a process for the selective hydrogenation of diolefins in liquid hydrocarbon fractions such as, for example, steam cracked gasolines.
  • liquid hydrocarbon fractions such as, for example, steam cracked gasolines.
  • These essences indeed contain gum-generating compounds that are diolefins mixed with olefinic compounds and aromatic compounds. To recover these olefinic compounds and these aromatic compounds, it is necessary to selectively hydrogenate the diolefins.
  • Such treatments are generally carried out on metal catalysts deposited on an amorphous or crystalline support.
  • the metals used are the Group VIII metals and among these, nickel and palladium can be noted.
  • the implementation of the hydrogenation operation itself involves a heat extraction system because the exotherm is such that the catalyst would be damaged by the excessively high temperatures which prevail at the outlet of the catalyst bed.
  • This extraction of calories can be done by exchange with a heat transfer fluid in a reactor-exchanger, the catalyst being maintained in the tubes and the heat transfer fluid being debited from the grille side.
  • Such an implementation, called isothermal is complicated and requires the use of very expensive reactors.
  • An improvement consists in separating the catalyst into two beds and cooling the effluent from the first bed with a quenching liquid consisting of cold hydrogenated product.
  • the object of the invention is therefore to extend the operating time of the catalyst payload by gradually bringing the entire catalyst charge into service instead of using it entirely from the start. It has in fact been surprisingly found that it is better to use the minimum quantity of catalyst rather than having a substantial excess at the start of operation, as is commonly done in order to compensate for the deactivation of the first part. bed.
  • the process which is the subject of the invention therefore consists in distributing the catalyst into several beds and preferably in the same reactor, but putting these beds into service successively, by adding a new catalyst bed at the head as soon as the need arises. is felt, that is to say when the performance of the mass of catalyst in operation is insufficient to give a product to the specifications.
  • the invention is a process for the hydrogenation of hydrocarbon feedstock by contact with p catalytic beds n 1 ... n i ... np, said beds being separated and containing the same catalyst, process characterized in that the feedstock is introduced into the bed n p and the resulting product p p is extracted, that, when the product p p does not reach the required quality, the introduction of the load in bed np is stopped, and that simultaneously the load is introduced into bed n p-1 , the product obtained p p-1 being introduced into bed n p , and that then, generally, when the product p p reaches the minimum performance threshold, the introduction of the load into the bed ni is stopped, at the same time the load is introduced into the bed n i-1 , the product obtained p i-1 being introduced into the bed n i , and so on until i has taken all the integer values up to 1.
  • FIG. 1 represents the process applied with several separate reactors, FIG. 2 in a single reactor.
  • the known technique consisted in using an entire mass of catalyst to obtain a product p p having the required specifications, for a cycle time D (or operating time).
  • the mass of catalyst or an amount less than this mass is divided into p beds (n 1 , n i , n p ) distributed in 1 or more reactors and each containing at least the minimum quantity of catalyst necessary for obtaining the required specifications.
  • the supply of the load is moved to the bed n i-1 , located upstream of the bed nor so that the load to be treated successively crosses the bed n i-1 of new catalyst, then the product from this bed through the spent catalyst bed ni, the product obtained pi passing through the spent catalyst bed n i + 1 etc ... until the bed np either crossed, the product p p then being obtained.
  • valve 40 when p 4 reaches its threshold S, the valve 40 is closed (preferably progressively), thus stopping the introduction of charge into n 4 and in the same time, the valve 30 is open so as to supply the bed n 3 with the load via the pipe 3.
  • the product p 3 obtained after passage of the charge over n 3 , passes over the bed n 4 (downstream). It appears p 4 of bed no 4 .
  • the procedure is the same as above, forming the valve 30 while simultaneously opening the valve 20 for supplying the bed n 2 through the pipe 2.
  • the product p 2 from this bed then passes over the bed n 3 , the product p3 from n 3 passes over the bed n4 and the final product p4 is extracted.
  • the hydrogen necessary for the reaction is brought for example by means of the pipes 41, 31, 21, 11 successively put into service on the reaction beds.
  • the use of a single reactor is particularly advantageous in terms of costs, but the reactor can only operate with a downflow, the bed n p having to be the lowest and the bed n 1 the top.
  • the operator may also prefer to use smaller quantities of catalyst (total mass less than ) for comparable cycle times.
  • catalyst test unit comprising 4 reactors which can operate in series, the effluent from the first being transferred to the second then to the third and then to the fourth.
  • reactors modeling each bed consist of a steel tube 3 cm in diameter. Each of these reactors can be heated by an electric oven which makes it possible to maintain the desired temperature in each of the beds.
  • All of the reactors can be used as described above, that is to say N ° 1, N ° 2, N ° 3, N ° 4 but a device also makes it possible to use the reactor 4 only or else 3 and 4 in series, or 2, 3 and 4 in series.
  • catalyst LD 265 from the company Procatalyse containing 0.3% of palladium supported on alumina in the 4 reactors arranged in series at a rate of 100 cm 3 per reactor.
  • This catalyst is reduced by hydrogen delivered for 6 hours at 150 ° C at a rate of 40 l / h.
  • the performances are measured by the variation of the maleic anhydride index (AVM) between the inlet of the first reactor and the outlet of the fourth.
  • the temperature is set at 80 ° C in all of the reactors at the start of operation and then regularly increased to 120 ° C to restore the conversion when it decreases.
  • the load gives an AVM of 106, the AVMs of the products are given as a function of time as well as the operating temperature in table 1.
  • Table 1 Walking time in hours
  • Temperature MAV output 50 80 ⁇ 2 100 80 ⁇ 2 200 80 ⁇ 2 500 80 2.2 750 80 2.3 820 80 2.8 950 80 3.8 1160 95 ⁇ 2 1300 95 4 1400 110 ⁇ 2 1540 110 5 1600 120 ⁇ 2 1800 120 8
  • a new reactor is put into service when the assembly in operation no longer makes it possible to obtain an AVM of less than 3 at output for a temperature of 80 ° C. Then, the temperature of the four reactors is gradually increased to restore performance.
  • the AVMs of the products are given as well as the arrangement of the reactors and the operating temperature as a function of time in Table 2.
  • Table 2 Walking time in hours Arrangement Temperature MAV output 50 4 80 ⁇ 2 100 4 80 ⁇ 2 200 4 80 2.4 500 4 80 2.8 600 4 80 3.8 700 3.4 80 ⁇ 2 800 3.4 80 ⁇ 2 1000 3.4 80 2.5 1200 3.4 80 3.2 1300 2,3,4 80 ⁇ 2 1400 2,3,4 80 ⁇ 2 1600 2,3,4 80 2.7 1800 2,3,4 80 3 1900 1,2,3,4 80 ⁇ 2 2000 1,2,3,4 80 ⁇ 2 2200 1,2,3,4 80 2.5 2400 1,2,3,4 80 3.8 2800 1,2,3,4 90 ⁇ 2 2950 1,2,3,4 90 3.7 3000 1,2,3,4 95 ⁇ 2 3280 1,2,3,4 95 2.6 3300 1,2,3,4 100 ⁇ 2 3480 1,2,3,4 100 3 3500 1,2,3,4 115 ⁇ 2 2590 1,2,3,4 115 3.7 3600 1,2,3,4 120 ⁇ 2
  • catalyst LD 241 from the company Procatalyse containing 10% of nickel supported on alumina in the 4 reactors arranged in series at the rate of 100 cm 3 per reactor.
  • This catalyst is reduced by hydrogen delivered for 15 hours at 400 ° C at a rate of 40 l / h.
  • the activity of the catalyst is then measured under the same conditions as in Example 1.
  • the AVMs of the products are given as a function of time as well as the operating temperature in table 3.
  • Table 3 Walking time in hours Temperature MAV output 40 80 ⁇ 2 70 80 ⁇ 2 100 80 2 400 80 4.2 420 95 ⁇ 2 470 95 2.7 500 95 3.2 520 110 ⁇ 2 540 110 ⁇ 2 600 110 3.1 620 120 ⁇ 2 640 120 ⁇ 2 650 120 2.5 670 120 2.9 700 120 3.2
  • Table 4 shows the AVM of the products as well as the arrangement of the reactors and the operating temperature as a function of time.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP93400164A 1992-01-28 1993-01-25 Procédé d'hydrogénation sélective, notamment des dioléfines dans les essences de vapocraquage, avec un catalyseur sous forme de lits mis en oeuvre successivement Expired - Lifetime EP0554151B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9200992 1992-01-28
FR9200992A FR2686617B1 (fr) 1992-01-28 1992-01-28 Procede d'hydrogenation selective de charge hydrocarbonee avec des lets catalytiques mis en óoeuvre successivement.

Publications (2)

Publication Number Publication Date
EP0554151A1 EP0554151A1 (fr) 1993-08-04
EP0554151B1 true EP0554151B1 (fr) 1996-07-10

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP93400164A Expired - Lifetime EP0554151B1 (fr) 1992-01-28 1993-01-25 Procédé d'hydrogénation sélective, notamment des dioléfines dans les essences de vapocraquage, avec un catalyseur sous forme de lits mis en oeuvre successivement

Country Status (8)

Country Link
US (1) US5306852A (zh)
EP (1) EP0554151B1 (zh)
JP (1) JPH05247475A (zh)
CN (1) CN1045950C (zh)
DE (1) DE69303505T2 (zh)
ES (1) ES2093370T3 (zh)
FR (1) FR2686617B1 (zh)
IN (1) IN181752B (zh)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2720754B1 (fr) * 1994-06-01 1996-07-26 Inst Francais Du Petrole Procédé et installation pour le traitement par hydrogénation sélective d'une essence de craquage catalytique.
FR2724390B1 (fr) * 1994-09-08 1996-12-13 Inst Francais Du Petrole Hydrogenation selective de coupes hydrocarbonees renfermant des hydrocarbures monoinsatures et polyinsatures
US5954950A (en) * 1995-09-07 1999-09-21 Institut Francais Du Petrole Intensive hydrofining of petroleum fractions
FR2743079B1 (fr) * 1995-12-27 1998-02-06 Inst Francais Du Petrole Procede et dispositif d'hydrogenation selective par distillation catalytique comportant une zone reactionnelle a co-courant ascendant liquide-gaz
US5847251A (en) * 1996-02-12 1998-12-08 Catalytic Distillation Technologies Multibed transalkylator and process
EP0921179A1 (en) * 1997-12-05 1999-06-09 Fina Research S.A. Production of olefins
FR2970260B1 (fr) * 2011-01-10 2014-07-25 IFP Energies Nouvelles Procede d'hydrotraitement de charges lourdes d'hydrocarbures avec des reacteurs permutables incluant au moins une etape de court-circuitage d'un lit catalytique
FR2970261B1 (fr) * 2011-01-10 2013-05-03 IFP Energies Nouvelles Procede d'hydrotraitement de charges lourdes d'hydrocarbures avec des reacteurs permutables incluant au moins une etape de permutation progressive
EP2865440A1 (en) * 2013-10-28 2015-04-29 Haldor Topsoe A/S Process and reactor for exothermal reaction
WO2017130081A1 (en) * 2016-01-27 2017-08-03 Sabic Global Technologies B.V. Processes and systems for increasing selectivity for light olefins in co2 hydrogenation

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1306238A (fr) * 1961-10-19 1962-10-13 Shell Int Research Procédé de raffinage d'essences obtenues par craquage et contenant des diènes
US3705204A (en) * 1967-05-18 1972-12-05 Nippon Oil Co Ltd Process for recovering conjugated diolefins selectively from a c5 fraction
US3926784A (en) * 1973-08-22 1975-12-16 Gulf Research Development Co Plural stage residue hydrodesulfurization process with hydrogen sulfide addition and removal
NL191763C (nl) * 1979-09-26 1996-07-02 Shell Int Research Werkwijze voor ontmetalliseren van een koolwaterstofolie.
US4560815A (en) * 1983-04-25 1985-12-24 The Babcock & Wilcox Company Automated catalyst regeneration in a reactor
US4704492A (en) * 1986-12-24 1987-11-03 Mobil Oil Corporation Selective hydrogenation of acetylenic impurities in crude butadiene
GB8702654D0 (en) * 1987-02-06 1987-03-11 Davy Mckee Ltd Process

Also Published As

Publication number Publication date
FR2686617A1 (fr) 1993-07-30
CN1045950C (zh) 1999-10-27
DE69303505T2 (de) 1996-11-21
ES2093370T3 (es) 1996-12-16
DE69303505D1 (de) 1996-08-14
EP0554151A1 (fr) 1993-08-04
JPH05247475A (ja) 1993-09-24
CN1092756A (zh) 1994-09-28
FR2686617B1 (fr) 1994-03-18
US5306852A (en) 1994-04-26
IN181752B (zh) 1998-09-12

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