JPS58142977A - Manufacture of high octane gasoline in catalytic decomposition device - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a process for improving the octane number of gasoline produced by fluid catalytic cracking of gas oil feedstocks using zeolite cracking catalysts with low sodium content.

Gasoline production by fluid catalytic cracking (FCC) of a hydrocarbon charge involves circulating and contacting the charge with a granular solid cracking catalyst at a cracking temperature to convert the charge components into low-normality reconstituted hydrogen through cracking. At the same time, deactivated carbonaceous contaminants are deposited on the catalyst. Gasoline is recovered from the conversion product.

Optionally, hydrocarbons are stripped from the catalyst particles by steam before the activity of the contaminated catalyst is regenerated by combustion of the carbonaceous deposit. The regenerated catalyst is further contacted with a bulk charge of hydrocarbon, and after repeated cycles of contact with the charge and regeneration, the regenerated activity of the catalyst declines. By replacing a portion of the total catalyst with fresh catalyst having an activity above the equilibrium value, the average activity of the total catalyst is maintained at a substantially constant equilibrium value.

A process has been proposed for improving the octane number of gasoline from FCC units using an ultrastable zeolite cocatalyst, preferably free of minerals, in the cracking catalyst composition. British patent number 2
．． No. 022,480 is cited as a reference.1 Ultrastable'' refers in the present invention to a type of synthetic crystalline aluminosilicate zeolite with a low sodium content.

The impact of exchangeable cations on catalytic cracking activity is discussed by Julius Schierzer and Ronald E., Ritter, W., L/Reis, I'd, Entl., Chetyh, Pr.
od, Rag, Daν, ;L! .

a, 1 io/exchanged ultrastable Y zeolite of Gio (1978), 8. ``Gas-oil decomposition over rare earth exchanged ultrastable Y zeolite'' (Re-H-Uα) is described in
It has been shown to be more aqueous for degradation than the ultrastable zeolide <11-USY>1, but even Re-H-USY is less active than the typical Re-H-Y zeolite.

It has been shown to have a higher concentration than Re-H-YkiH-USY zeolite due to the Bronsted acid position. The authors investigated the conversion rate of the low-density yb olefin at the second acid position of USY enzyme to paraffin and the aromatic condensed polynomial compound (
It has been shown that olefins and aromatics can be diffused and released from the zeolite by reducing the conversion to coke (coke). The exchange of rare earth elements into H-USY zeolite is
It tends to increase the transfer reaction rate, producing more coke and increasing the conversion rate. The authors do not mention the effects of strium exchange or flea contamination, which would reduce hydrogen-transfer reactions and lower conversion rates.

Until the present invention, catalysts with low sodium contents that promise octane enhancement to the desired results in industrial FCC units have not been available, and the present invention involves contacting the hydrocarbon charge with a granular solid cracking catalyst containing zeolites at cracking temperatures. Converting the feedstock components to low-boiling hydrocarbons, including gasoline fractions, by decomposition and simultaneously depositing inactivated carbonaceous contaminants on the catalyst, gasoline is recovered from the conversion product, and optionally the catalyst is steam stripping the hydrocarbons from and burning carbonaceous deposits on the contaminated catalyst to regenerate the catalyst's catalytic cracking activity;
and the regenerated catalyst is further contacted with a charge, and the activity of the catalyst decreases due to repeated cycles of charge contact and regeneration, but the fresh catalyst has an activity above a substantially constant equilibrium value which is a fraction of the total catalyst. In the gasoline production process by catalytic cracking of the above-mentioned charge, in which the average activity of the total catalyst is kept at the above-mentioned equilibrium value by substitution with The alkali content of the hydrocarbon charge is kept below Q, 5 p'ia, and the alkali metal oxides of the equilibrium catalyst are kept below 8.0 p'ia of the zeolite of the catalyst under fresh catalyst conditions. The present invention relates to an improved method for maintaining high octane numbers of the gasoline over repeated cycles of catalyst contact and regeneration through ripping and regeneration.

The present invention uses fresh zeolite catalyst particles having an alkali metal oxide content of about 1.51 or less, based on the zeolite content, and the alkali metal oxide content of the equilibrium catalyst is 2.0 or less, based on the weight of zeolite in the fresh zeolite catalyst. The octane number of the gasoline fraction from the cracker is increased over repeated cycles of charge cracking and regeneration by adjusting the amount of alkali metal oxide that contacts the total catalyst through weight-like cracking, stripping, and regeneration. It provides a method for improving the operation of FCC equipment to maintain standards.

In a preferred embodiment of the present invention, the fresh catalyst is prepared by (G) ion-exchanging synthetic sodium faujasite with ammonium ions and leaving residual sodium as is, (b) calcining and ( 6) It is produced by ion-exchanging 11-calcined zeolite with ammonium ions to reduce the sodium content. The catalyst also contains an inorganic matrix component that can be mixed with the faujasite before or after steps (8), (6) and (6).

Conventional technology uses decomposition catalysts)
There is a lack of awareness that this affects the octane number of CC equipment gasoline and the need to control the contact of low sodium content zeolite catalysts with sodium or other alkali metals during use in FCC equipment to preserve the octane improving ability of low sodium content zeolite catalysts. Not recognized.

Applicants' findings are unexpected in light of the disastrous delivery of the Scherzer and Ritter literature cited above.

Contrary to popular claims in the literature, we have found that while sodium contamination actually reduces coke production and lowers conversion, sodium contamination also reduces olefin yield and lowers gasoline octane number.

Catalyst particles useful in the practice of this invention include H-zeolite, NH
, - zeolites, Re0 - zeolites, and mixtures thereof, the catalyst comprises about 5 by weight based on the weight of the zeolite in the fresh catalyst - or less rare earth particles. Contains oxides. In particularly preferred embodiments, the zeolite in the fresh state is about 8480 to 84.
Synthetic faujasite with a single cell size a) in the range of 76.4. The catalyst particles in the fresh (unused) state contain not more than 1.5 Nano (or equivalent amount of other alkali gold II4) based on the weight of the zeolite component, provided that the amount of zeolite component is measured by 2-@ Typically, the amount of catalyst particles is 5 to 80% by weight. The fresh catalyst particles have a weight of less than 1.0, preferably 0, based on the weight of the zeolite component.
．． It is preferable to use a material containing Nano or an equivalent amount of other alkali metal oxides of 5 times or less. It is therefore necessary that both the zeolite or non-zeolite (substrate) component(s) have a very low content of sodium and other alkali metals.

The inorganic oxide components of the catalyst particles include, for example, synthetic silica-alumina, naturally occurring clays, modified clays, and their like with inert additives known in this field and utilized as decomposition catalyst components to improve activity, selectivity, etc. A mixture may also be used. Typical catalysts used are British Patent No. 2.022.489 and US Pat. No. 944,800, No. 058.484.
It is as described in the issue. U.S. Patent No. 8.506
．． The low sodium content produced by the method of No. 594 is recommended.

The catalyst of the present invention is put into service in a conventional FCC unit using conventional operating conditions. The present invention may also be practiced under stripping and regeneration conditions that vary from conventional conditions. Typical conditions for FCC are described in US Pat. No. 8,944,482.

The practice of the present invention removes deposits of sodium oxide and/or other alkali metal oxides from fresh, low sodium content zeolites of about 0.5 weight or more based on the weight of the zeolite component of the fresh catalyst during all stages of use. For use on all catalysts.

Sources of alkali metals that contact and are deposited on the recycled catalyst during recycling through the reactor (cracker), stripper, and regenerator include salts carried with the crude oil to the refinery. At the source of the salt, the salt in the crude oil is usually larger than the base amount that enters the refinery by salting during transportation, etc. For the purposes of the present invention, the alkali metal, and therefore the salt content, from any source, including the alkali metal in the treated water that comes into contact with the catalyst (e.g. with the feedstock, during stripping or regeneration), is considered to be in the fresh catalyst. If necessary, it is necessary to adjust by desalination so that the amount does not exceed 2.0 weight t* based on the weight of zeolite. If necessary, conventional crude oil desalination methods can be used or the FCC feedstock can also be desalted. The known desalination method is written by Nelson, published by Matsuku Grow-Hill Publishing '''PetroleumRef-4nary
Engineering”, 4th edition, page 66-288, 1958. Other desalination methods can also be used.

Processes that introduce caustic soda into the FCC capping feedstock or where it comes into contact with all recycled catalyst should be avoided.
IJ loading should be adjusted to a minimum. The other alkali metals (potassium and lithium) should be adjusted as well. The hydrocarbon feedstock or water entering the reactor must not be contaminated by the potassium hydroxide used in the alkylation unit.

The present invention will be more fully demonstrated and the advantages will be realized by the following examples.

All rare earth-free 5FCC catalysts were tested to determine the effect of sodium on octane. The catalyst used in Test I was repeatedly contacted with an ammonium salt solution to exchange easily exchangeable sodium ions by the method described in U.S. Pat. Further, the alkali metal oxide content was reduced. A fluid cracking catalyst containing hydrogen faujasite (z4/6zλ cell size) 21- was found to contain 0.20 heavy I- of Na2O as determined by X-ray diffraction analysis.The substrate was an amorphous material obtained from kaolin clay. It was silica-alumina.

From Tests 8 to 4, the sodium oxide content of the catalyst increased as follows. The catalyst of Run 5 was repeatedly contacted with an ammonium salt solution to reduce Na2O and further exchanged without calcination to reduce the sodium oxide content by the method described in US Pat. No. 8,606.594. The fresh catalyst used in test 5 was x-w[! ! The zeolite content as determined by Im is 25-, and the zeolite single-cell size is 24-. ? It was 5λ.

A sample of the primary cracking catalyst was steam treated (1001 g steam) at 1450'F for 4 hours and used for gas oil cracking in an Fcc pilot unit.

The same batch of fluidized cracking catalyst used in test 1 (hydrogen faujasite 21%, cell size 24.62
;, 7 VIS, 0 0.20 wt.
aOHl? A slurry was made with a solution containing 5 ml. The slurry was stirred at 180"F for 45 minutes and then heated. The solids were then washed with water and dried. The resulting catalyst had a Na!O content of 0.84 wt. and was free of volatiles. (V.

Fi this catalyst at normal pressure, 1001! 1450” in steam
8898 g of the same non-steam treated batch sample of the fluidized catalyst used in the test IK was treated with H, 02658 ml and Na for 4 hours and used for gas oil cracking in FCC pilot acid.
Moisten and mix with a solution of OH159. Dry the impregnated catalyst with N
a, 0 content was 0.44 weight. This catalyst is 145
It was steamed at 0°F for 4 hours and used for gas oil cracking in an FCC pilot unit.

Jul Test Another sample of the Okaji batch of IK cracking catalyst was steamed at 1450°F for 4 hours. The prepared catalyst 84059 was impregnated with a solution of 15 g, ogoisal and NmOH 1511. This is dried and the Nano content is o, so
mii-tona'). This catalyst was used for gas oil cracking in an FCC pilot unit.

Test 5 An FCC catalyst sample containing about 25-zeolite without rare earths and 058 mNa*O was heated at 1450°.
Steam treatment was performed with F for 4 hours.

The conditions and gasoline octane numbers of the above five samples are shown in the table below. Pilot unit conditions were kept the same so that the conversion affected gasoline octane as little as possible.

The results show that gasoline 110N and MON were adversely affected in all cases when poisoned with sodium.

Shown in Tests 2.8 and 4. In fact, based on the zeolite content, Na, (compared to Test 5 with J L82%)
Based on the zeolite content, the higher octane of gasoline produced with a catalyst containing ``at 0 0.951&quot;
The former sodium contamination disappeared when the O content exceeded 1.62 wt.

The results in the table show that in order to preserve the octane-enhancing ability of low-sodium R-faujazite catalysts, it is necessary to prevent sodium deposition thereon during catalyst use.

Applicants' findings indicate that the deposition of even small amounts of NaHO (0.5% by weight based on the zeolite content) has a deleterious effect on octane. Na, OO, 5F in gas oil feedstock
+7um toxicity (catalyst Na, oo, imulto)
It is estimated that. Therefore, the sodium charge to the FCC unit should be kept below 0.5 ppt4 of the feedstock.

41H'Flfj Applicant Engelhard Koborein Yong Representative Patent Attorney Ryoji Kawase''''.

＞、：　、。

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Claims (1)

[Claims] 1. A hydrocarbon charge is brought into contact with a granular solid decomposition catalyst containing zeolite at a decomposition temperature to decompose and convert the charge components into low-boiling and pentahydric hydrocarbons including gasoline fractions. Simultaneously depositing inert carbonaceous contaminants on the catalyst, recovering gasoline from the conversion products, optionally steam stripping the hydrocarbons from the catalyst, and burning the carbonaceous deposits from the contaminated catalyst. The catalytic cracking activity of the catalyst is regenerated and (the regenerated catalyst is brought into contact with the charge), whereby the activity of the catalyst declines due to repeated cycles of charge contact and regeneration, but the activity remains above the equilibrium value. In a process for catalytic cracking of hydrocarbons for the production of gasoline, which consists in maintaining the average activity of all catalysts at a substantially constant above equilibrium value by substituting a portion of the total catalyst with fresh catalyst having Using fresh catalyst particles with metal oxide content less than about L5 weight of zeolite content, keeping the alkali content of the hydrocarbon charge below 9.5 ppyx and keeping the alkali metal oxide content of the equilibrium catalyst fresh. A process characterized in that the amount of alkali metal oxide in contact with the total catalyst is reduced by decomposition, stripping and regeneration so as to maintain the amount of alkali metal oxide to be less than 2.0% by weight based on the zeolite weight of the catalyst. 2. The fresh catalyst comprises a zeolite component selected from the group consisting of H-zeolite, NH,-zeolite and mixtures thereof.
ridge method. 8. The method of claim 1, wherein said zeolite is a synthetic faujasite with a single cell size t in the range of about 84.80 to 24.75 amps. 4. The above fresh catalyst is prepared by (a) ion-exchanging synthetic sodium faujasite with ammonium ions and leaving the residual sodium as is, (6) calcining so that the residual sodium can be exchanged later, and (e) ion-exchanging with ammonium ions. The claimed invention further comprises an inorganic oxide substrate component which is prepared by further reducing the sodium therein, wherein said catalyst also comprises an inorganic oxide substrate component which is mixed with said faujasite before or after steps (a>, (6) and (6)). The method according to any one of items 1 to 8. 5. Decomposition, steam treatment, and regeneration step Claims in which all the steam used to contact the biodegradation catalyst is substantially free of alkali metals. The method described in any of paragraphs 1 to 4.