AU698640B2

AU698640B2 - Catalytically converting a hydrocarbonaceous feed

Info

Publication number: AU698640B2
Application number: AU14438/97A
Authority: AU
Inventors: Krijn Pieter De Jong; Carolus Matthias Anna Maria Mesters; Antonius Franziskus Heinrich Wielers
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 1996-01-15
Filing date: 1997-01-14
Publication date: 1998-11-05
Anticipated expiration: 2017-01-14
Also published as: AU1443897A; ZA97249B; CA2241548A1; JP2000503330A; CN1208431A; AR005446A1; EP0882111A1; WO1997026313A1

Description

WO 97/26313 PCT/EP97/00200 CATALYTICALLY CONVERTING A HYDROCARBONACEOUS FEED The present invention relates to a process for the catalytic conversion of a hydrocarbonaceous feed comprising contacting the hydrocarbonaceous feed in a moving-bed reactor with particulate catalyst, to obtain reactor effluent and spent catalyst, separating spent catalyst from reactor effluent, regenerating spent catalyst in a regenerator by contacting spent catalyst with air unA'ir conditions to combust coke deposited on the catalyst to obtain regenerated catalyst which is supplied to the moving-bed reactor.

Such a process is called a fluid catalytic cracking process (FCC). In such a process the hydrocarbonaceous feed is catalytically converted into lighter cracked products which find application, for example, as motor fuels, diesel fuels, oils and chemical feedstocks. In the FCC process, the feed is contacted at elevated temperatures in the range of from 450 to 800 OC and a pressure in the range of from 0.1 to 1 MPa with a suitable particulate catalyst. The mass ratio of catalyst used relative to the feed to be converted is suitably in the range of from 3:1 to 100:1, and the contact time is suitably less than 10 seconds. The particulate catalyst suitably includes acidic molecular sieve crystals, clay and a binder. Such a catalyst is well known as such; a description of the catalyst can, for example, be found in Applicant's co-pending European patent application No. 95 201 948.7 filed on 14 July 1995. In the specification the term "molecular sieve catalyst" will b< used to refer tc this particulate catalyst.

In recent years it has become common practice to convert increasinaly high ,boling range hydrocarbonaceous

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WO 97/26313 WO 9726313PC'T/EP97/00200 feeds, which contain small amounts of metals such as nickel and vanadium. These metals will deuoosit on the catalys- particles in the coke formed. in the conversion.

When dur4 na regeneration coke is combusted, the metals are retai'ned on the catalyst particles. Vanadium has a detrimental effect on the stability of the molecular sieve employed in the catalyst, whereas nickel I's detrimental for the_ coke selectivitv and hydrocaen -make in that with an increasing nickel content more gaseous products, hydrogen and light hydrocarbons sucr. as methane, are formed and more coke is deposited on- the catalyst particles.

Applicant's co-pending Euro.pean patent appl--ctioln No. 95 2-1 948.7 filed on 14 July v Qrltst a process focr the catalytic cOnverS4 n of a hydrocarbcnraceous feed comprisi'. contacting the hydrocarbonaceous feed in a rnovi4nq-beI react-or withi particulate catalyst. The catalyst particles comprise a core surrounded by a shell, wherein the core is a moleculai- sieve catalyst., and wnerein the shell comnprises a substantially non-acidic meso)- ori macroporcous- oxidic oroxyanionic material.

These catalyst particles were: prepared ily co ntactin4 freshly Trepared molecular sieve :aavtcr~lswith a coatinu fluid containing pre:cursois ol a bsnill non-acidic mesc- or macroporous oxidil: I- xvanionic material.

Aplicant now had found that durir ot hc PC- process the detrimcntal effect of an acuml:io f metals_ which takes Llace can be countered whe-n spe.-. catalyst_ _is treated wit', this coat-inq fluid.

Therefore the present invention relatesito a rcess for thoe catalytic conversiona of- a hyrcabnceu ered comprisIg contacting th yrcrolme.$ eea :n a moving-bed react or with oarticulate aayst ot_ WO 97/26313 PCT/EP97/00200 3 reactor effluent and spent catalyst, separating spent catalyst from reactor effluent, regenerating spent catalyst in a regenerator by contacting spent catalyst with air under conditions to combust coke deposited on the catalyst to obtain regenerated catalyst which is supplied to the moving-bed reactor, wherein at regular intervals spent catalyst or regenerated catalyst is contacted with a coating fluid comprising precursors of a substantially non-acidic meso- or macroporous oxidic or oxyanionic material.

The coating fluid is a suspension of the precursor in a gas or in a liquid solvent, and suitably it is a colloidal dispersion of the precursor, which dispersion is also referred to as an aerosol (dispersion of solids in a gas) or a sol (dispersion of solids in a liquid solvent).

During coating the catalyst particles are hot, and when the hot particles are contacted with the coating fluid in the form of a dispersion of precursor in gas, the precursor will be deposited on the catalyst particles and a shell of a substantially non-acidic meso- or macroporous oxidic or oxyanionic material is formed. When the hot catalyst particles are coated with the coating fluid, the solvent will evaporate and a shell of a substantially non-acidic meso- or macroporous oxidic or oxyanionic material is formed.

The amount of coating fluid should be so selected that sufficient precursor is available to obtain a shell having a thickness in the range of from 0.05 to 20 micrometer.

Suitable non-acidic mesoporous oxidic or oxyanionic material include non-acidic oxidic or oxyanionic compounds of elements selected from groups 2A, 2B, 3A, 3B, 4A, 4B and the lanthanide series of the Periodic Table of Elements, for example clays such as kaolin and

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WO 97/26313 WO 9726313PCT/EP97/00200 -4 meta-kaolin, alumina, silica, maqmaesia, calcin, t:itania, zircoaia, yttria, ceria, lanthana. tin oxide-, alum.-naum phosphate, magnesium aluminate, and mIxtuies thereof.

Examples of macroporous oxidic or oxyanionic material include alpha-alumina and silica, for example in the form of amorpohous silica.

in the specification and in the claims the term "microporous material" is used to refer to a materal having pore sizes 3-f smaller than 1.0 nm (nanomet-er) and suitably in the range of from 0.3 to 0.9 nm, he term "macroporous material" is used toi refer to a material having pore sizes greater than 50 nm and suitab.ly greato,_r than 100 nm., and the term "'mesoporous material" T is used to refer to a material having oeszs hc r between the pore sizes of micronorous material and the pore size or macroporous material.

The spent or regenerated catalyst Daryt4_leo can b-e contacted with the coating liquid in several, ways, the coating liquid can be sprayed into the regenerator or it can be injected into the transport conduits extending t-he reactor and the regenerator.

Alternatively a side-stream of reqeneratel rataly st can be removed from the regenerator and paos-d a separate vessel provided with means rae Lrinq normal oneraticn, ax fluidized! he-t in the- vessel_. The coating liquid is then sprayed into vess-e and coated catalyst particles are withdrawn vessel.

In examples IA through ii of .7 Liicant's c-peno.:ng Huropean patent application No .i 201 9449_7 =ni _n the below exampie coating liquids arg wnic- can he used in the present ainventc Wit !cim o skilled nerson will be able to( p> ,iui that will' %ield the subs tant iall -1 acid ml-r macroporous oxidic or oxyanionic mt_rrAl uner he conditions nrevailing in his F-C process.

WO 97/26313 7/6 13PT/EP97/0020) The invention will now be oescribel b.y way cf- example in more detail with reference tc- tne toileIwing examples.

In the examples particulate catalyst was (contacted with a feed described in Table 1 in a micro-act.ivity testing unit at a temperature of 540 0 c and at atmospheric pressure.

Table I. C-ompcsition of t-he feed used in the examples, in the Table, %m denotes per cent by mass and ppmmr denotes parts per milli on baecn mass.

Gravity, API 21.3 Hydrogen, Sulphur, sr )m ?r N it-r o ge n, 9Om 0 Vanadium, ppmm 86 Nickel, ppmm Conradson Carbon, %m 3.66 Kinematic viscosity at 100 0 C, mm'2/s 1 Aromatic Carbon, 15.5 In the examples use was mnade of- tp~~ raalysI,- n the form of' thae Advanc, R927 catays-t- fromr AKZ-) Nobel which had been- sampled fromr a comrmercialI F7,- unit-. The spent catalys:. contained appioxima*tely I -rrl oke-. A batch of this- spent catalyst was used as such in the example not- accorndina to the invention, anid in the example accordinco to the inverticn a b:atch of this spent catalyst coate3 w~tn silic-a was used (tnis cata vst4is referred to as ccate:-d spent cat-) Prior to thae test in t-he mc-act ivi ty t---tlnu U1,I t: the spenL c1s w-as, tr-at ed r~mc hydrocarbonaCeous deposits.

The coat ini py'ccedure t manul actur .tecae spent catalyst was us f:-Ilows An amo~unt o 0 ia the s'rercatalyst was l-oade-d in. a spraTy coxatin, pprano model WO 97/26313 WO97/23 13 C'r/IP97/00200 STREA- 1 manufactured by Niro -Aero~mat. Fielder. Thie solids were fluidized in an air flo hAvin a temoerature of 80 OC at the inlet. An amount of 3E)4 gram of an aqueous silica sol, Nyacol 2040NH4 (containing 40 of,,silica) was sprayed inf-o the fluidized bed a rate of- G0O nil/minute using an atomizing pressure of 2 bar to spray the liquid through a nozzle having an outlet opening with a diameter of 0.5 mm. The product was dried in a separate furnace at 120 In air f or 2 ho urs and subs equent Iv calcined for 2 ho--urs at 550 in air, followed by a treatment at: 600 OC in air to remove any hydrocarbcnaceous deposits. The rouc so o-btained is the coated spent catalyst sample acco)rding the invention.

The effect- of the coat ing is a re-duced coke yield! and a reduced yie-ld of gaseous, component, hydroqen and methane, as can be, seen from mabe and 3.

Table 2. Coke yield as a -function of temass ratio of catalyst to the feed (C/o i n ka/kg wherein thg- coke yield is in '6m based on temass or the f eed.

coke v Ie..o C/o Spent catalyst Coatedi spent ca, 1.87 V. 14 1. 95 2.62 'IA7? 2.74 9.26 3 .54 0. 03 3 .83 9 .5 5 4.59 11 4.81 5.60 1> 6.70 WO 97/26313 WO 97/63 13PCTIEP97OO200 7 Table 3. RatJio of hydrogen yield ri n, t yield as function of the nc:t conversion., whlich the sum cf yield of gaseous components and graso~lin- ,(In b-asedi on the f eed).

Net conversion 35.24 37.55 42.99 44.07 51.66 S55.82 7.0 6 58.03 62.22 hydrogen yield Spent catalyst 0.5128 metharie yield oated srent cat 0 .5714 0 666C,7 0676? 5 102 0.5 728 0.6 10 2 0.65 Tables 2 and 3 clearly illustrate thle beneficial effect of coatinu spoent catalyst during the FCC- Process.

Now

Claims

1. Process for the catalytic conversion of a hydrocarbonaceous feed comprising contacting the hydrocarbonaceous feed in a moving-bed reactor with particulate catalyst, to obtain reactor effluent and spent catalyst, separating spent catalyst from reactor effluent, regenerating spent catalyst in a regenerator by contacting spent catalyst with air under conditions to combust coke deposited on the catalyst to obtain regenerated catalyst which is supplied to the moving-bed reactor, wherein at regular intervals spent catalyst or regenerated catalyst is contacted with a coating fluid comprising precursors of a substantially non-acidic meso- or macroporous oxidic or oxyanionic material.

2. Process for the catalytic conversion of a hydrocarbonaceous feed substantially as hereinbefore described. Dated 10 August, 1998 Shell Internationale Research Maatschappij B.V. Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON 0 S [n:\libc]03965:MEF I INTERNA'fI()NAL SICARCI REIPO)RT fite PCT/EP 97/00200 A, (LASS[11'ATioO(f- S(l l3F:(71MAIER IPC 6 ClOG11/18 B01J38/68 According to International [latent Classification (111C( 3 r to both national classitication and jjP( FIELDS SFARCflE' Minimum documentation searched (classificationi %ystemn foltowed byv dassilicati %ymbolIs) IPC 6 ClOG B01J Documentation searched other than nirmumn documiientationf to the extent that such documents are included in the fields searched Flectronic data base consulted during the internrational Search (name ol data hase and, where practical, search terms used) C. DOCUIMENTS CONSIDERED) To BE Category Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. A US 5 232 885 A (AMOCO)

3 August 1993 [El Further dncuenents are listed in the continuation of hox C. [ox Patent famiuly members are listed tn annex. Special categories of cited documents later document published alter the international tiling date oir prionty date and noit in coniltect with the application hut WA document defining the general state of the arc which is not cited to unders;tand the principle or theotr,, underlying the considered to he of particular relevance invention earlier document but published on or alter the international X. document of particular relevance; the claimed invention filing date cannot he considered novel or cannot be considered to document which may thanw doubts on priorty claim(s) tic involve an inventive step when the document is taken alone which is cited to establish the publication date of another 'Y document of parts ilar relevance; the claimed invention citation or other special reason (as specified) cannot be consi,- to insolve an inventive step when the document referrng to an oral disclosure, use, exhihition or docum!nt is comicd with one iir more other such disco- other means ments, such comhination heing obvious to a person skilled *P document published prior to the intemational filing date hut in the art. later than the piority date claimed W document member of the same patent lamily [)ate of the actuial completion of the international search Date of mailing of the international search report

4 April 1997 11. 04.97 Name and mailing address of the ISA Authoized otlicer European Patent 0Office, P. B. 58 18 Patentlaan 2 NL 2280 fly Rilswitk Tel. (+31.70) 340-2040, T'x. 31 651 cpo WI,Mic eIs p Fax: 31-70) 34,0-3016 ihes P Form PCT:ISA.Si0 (second sht)t (July 1992) INTILANATIONAL SEARCH R14,3ORT Inter, iul Apphi -ion No. information on patent (anruly membr PC EP 9 7/00200 Patent document [llcan atent family Publication ctied in scarch report daememberls; date US) 5232885 A 03-08-93 NONE Form PCT4.SA 210 (patent (arnily anlneal (July 1992)