CA1231661A - Process for upgrading a gasoline - Google Patents
Process for upgrading a gasolineInfo
- Publication number
- CA1231661A CA1231661A CA000454439A CA454439A CA1231661A CA 1231661 A CA1231661 A CA 1231661A CA 000454439 A CA000454439 A CA 000454439A CA 454439 A CA454439 A CA 454439A CA 1231661 A CA1231661 A CA 1231661A
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- Prior art keywords
- silicate
- fraction
- sio2
- mixture
- molar ratio
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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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A B S T R A C T
PROCESS FOR UPGRADING A GASOLINE
A complete gasoline fraction obtained by catalytic cracking, which has an aromatics content of a %w and consists of a light, a middle and a heavy fraction, said heavy fraction having an aromatics content of b %w such that 0.35 < ? < 0.45, is upgraded by separating the mixture of light and middle fraction from the product obtained by catalytic cracking and contacting this mixture or a part of it with a crystalline metal silicate which after one hour's calcination in air at 500°C has the following properties:
a) an X-ray powder diffraction pattern in which the strongest lines are the four lines mentioned in Table A,
PROCESS FOR UPGRADING A GASOLINE
A complete gasoline fraction obtained by catalytic cracking, which has an aromatics content of a %w and consists of a light, a middle and a heavy fraction, said heavy fraction having an aromatics content of b %w such that 0.35 < ? < 0.45, is upgraded by separating the mixture of light and middle fraction from the product obtained by catalytic cracking and contacting this mixture or a part of it with a crystalline metal silicate which after one hour's calcination in air at 500°C has the following properties:
a) an X-ray powder diffraction pattern in which the strongest lines are the four lines mentioned in Table A,
Description
PROCESS FOR UPGRADING A G~SDLINE
The invention relates to a process for upgrading a gasoline obtained by catalytic cracking.
Gasoline obtained by catalytic cracking has a high olefins content, which is the reason why it shows a tendency to gumminess.
Furthermore gasoline obtained by catalytic cracking has a relatively low aromatics content, which is the reason why it has a relatively low lane number. On account of the aforementioned properties it is preferred to subject gasoline obtained by catalytic cracking to an upgrading treatment before using it as a mixing component for motor gasoline. In this treatment it is important that the C5+ hydrocarbon fraction remains as large as possible since the yield of normally gaseous hydrocarbons should be limited.
Recently, novel crystalline metal silicates of a special structure were synthesized which show catalytic activity in the conversion of non-arcmatic organic compounds, such as olefins, into aromatic hydrocarbons. The catalytic performance of these silicates is to a great extent insusceptible to the presence of Selfware and nitrogen compounds in the feed. The crystalline metal silicates concerned are characterized in that after one hour's calcination in air at 500 C they have the following properties:
a) an Era powder diffraction pattern in which the strongest lines are the four lines mentioned in Table A, TABLE A
do lull + 0.2 l0.0 + 0.2 3.84 _ 0.07 Jo Ed 3.72 + 0.06, and Jo 3~66~L
b) in the formula which represents the composition of the silicate expressed in moles of the oxides and which, in addition to Sue, includes at least one member chosen from the group consisting of Foe and Allah, the SiO2/tFe203 + Aye) molar ratio is higher than lo An investigation into the use of the above-mentioned crystalline iron, aluminum, and iron/aluminium silicates as catalysts for upgrading a gasoline fraction such as it occurs in a product obtained by catalytic cracking has shown that although, generally, by using crystalline silicates belonging to this group a reduction of the olefins content as well as a rise in the aromatics content can be achieved, there are a number of cases in which the results obtained are not good enough to decide to use them on a technical scale. The investigation has shown that, on account of the activity, selectivity and stability which the-above-mentioned crystalline metal silicates show when used for upgrading a gasoline fraction such as it occurs in a product obtained by catalytic cracking, they can be divided into three classes.
Class I comprises the iron silicates and iron/aluminium silicates having a Sophie molar ratio lower than 250 and a Sue mylar ratio of at least S00.
Class II comprises the aluminum silicates and iron/aluminium silicates having a Sue molar ratio lower than 500.
Class III comprises the iron silicates, aluminum silicates and iron/aluminium silicates having a Sophie molar ratio of at least 250 and a Sue molar ratio of at least 500.
The crystalline metal silicates belonging to class I have sufficient activity, selectivity and stability and are therefore suitable for use such as they are. The crystalline metal silicates belonging to class II have sufficient activity and selectivity, but insufficient stability. The crystalline metal silicates belonging to class III have insufficient activity.
,. .
~Z3.~6~,~
The crystalline metal silicates belonging to classes II and III
cannot therefore be used such as they are.
Further investigation into this subject has resulted in three measures which have an extremely favorable influence on the selectivity or the stability of the catalysts mentioned herein before. The invention relates to the application of these measures (hereinafter referred to as measures 1-3) either individually or combined. Since these measures are unable to improve the activity of the catalysts mentioned herein before, the metal silicates belonging to class III, which have insufficient activity, will not be considered here.
Measure l relates to the use of a mixture of two catalysts, one of which is the crystalline metal silicate. Measure l leads to considerable enhancement of the selectivity.
Measure 2 relates to the use of the metal silicate with a heavy fraction, which fraction has a given aromatics content and has been separated by distillation from a gasoline fraction present in the product obtained by catalytic cracking. Measure 2 leads to considerable enhancement of the selectivity.
Measure 3 relates to the use of the metal silicate with a mixture of a light and a middle fraction, which mixture has a given aromatics content and has been separated by distillation from the complete gasoline fraction present in the product obtained by catalytic cracking. By the complete gasoline fraction is meant the C4+-fraction with such a boiling range that 98 ow of the gasoline is recovered at a temperature between 180 and 250 C. Measure 3 leads to such an improvement of the stability that metal silicates belonging to class II, which as such have insufficient stability, are now suitable for use. Measure 3 is also suitable for metal silicates belonging to class I. These metal silicates show sufficient stability in themselves, but the use of measure 3 adds still considerably to their stability. If desired, measure 3 can be cabined with measure l and/or measure
The invention relates to a process for upgrading a gasoline obtained by catalytic cracking.
Gasoline obtained by catalytic cracking has a high olefins content, which is the reason why it shows a tendency to gumminess.
Furthermore gasoline obtained by catalytic cracking has a relatively low aromatics content, which is the reason why it has a relatively low lane number. On account of the aforementioned properties it is preferred to subject gasoline obtained by catalytic cracking to an upgrading treatment before using it as a mixing component for motor gasoline. In this treatment it is important that the C5+ hydrocarbon fraction remains as large as possible since the yield of normally gaseous hydrocarbons should be limited.
Recently, novel crystalline metal silicates of a special structure were synthesized which show catalytic activity in the conversion of non-arcmatic organic compounds, such as olefins, into aromatic hydrocarbons. The catalytic performance of these silicates is to a great extent insusceptible to the presence of Selfware and nitrogen compounds in the feed. The crystalline metal silicates concerned are characterized in that after one hour's calcination in air at 500 C they have the following properties:
a) an Era powder diffraction pattern in which the strongest lines are the four lines mentioned in Table A, TABLE A
do lull + 0.2 l0.0 + 0.2 3.84 _ 0.07 Jo Ed 3.72 + 0.06, and Jo 3~66~L
b) in the formula which represents the composition of the silicate expressed in moles of the oxides and which, in addition to Sue, includes at least one member chosen from the group consisting of Foe and Allah, the SiO2/tFe203 + Aye) molar ratio is higher than lo An investigation into the use of the above-mentioned crystalline iron, aluminum, and iron/aluminium silicates as catalysts for upgrading a gasoline fraction such as it occurs in a product obtained by catalytic cracking has shown that although, generally, by using crystalline silicates belonging to this group a reduction of the olefins content as well as a rise in the aromatics content can be achieved, there are a number of cases in which the results obtained are not good enough to decide to use them on a technical scale. The investigation has shown that, on account of the activity, selectivity and stability which the-above-mentioned crystalline metal silicates show when used for upgrading a gasoline fraction such as it occurs in a product obtained by catalytic cracking, they can be divided into three classes.
Class I comprises the iron silicates and iron/aluminium silicates having a Sophie molar ratio lower than 250 and a Sue mylar ratio of at least S00.
Class II comprises the aluminum silicates and iron/aluminium silicates having a Sue molar ratio lower than 500.
Class III comprises the iron silicates, aluminum silicates and iron/aluminium silicates having a Sophie molar ratio of at least 250 and a Sue molar ratio of at least 500.
The crystalline metal silicates belonging to class I have sufficient activity, selectivity and stability and are therefore suitable for use such as they are. The crystalline metal silicates belonging to class II have sufficient activity and selectivity, but insufficient stability. The crystalline metal silicates belonging to class III have insufficient activity.
,. .
~Z3.~6~,~
The crystalline metal silicates belonging to classes II and III
cannot therefore be used such as they are.
Further investigation into this subject has resulted in three measures which have an extremely favorable influence on the selectivity or the stability of the catalysts mentioned herein before. The invention relates to the application of these measures (hereinafter referred to as measures 1-3) either individually or combined. Since these measures are unable to improve the activity of the catalysts mentioned herein before, the metal silicates belonging to class III, which have insufficient activity, will not be considered here.
Measure l relates to the use of a mixture of two catalysts, one of which is the crystalline metal silicate. Measure l leads to considerable enhancement of the selectivity.
Measure 2 relates to the use of the metal silicate with a heavy fraction, which fraction has a given aromatics content and has been separated by distillation from a gasoline fraction present in the product obtained by catalytic cracking. Measure 2 leads to considerable enhancement of the selectivity.
Measure 3 relates to the use of the metal silicate with a mixture of a light and a middle fraction, which mixture has a given aromatics content and has been separated by distillation from the complete gasoline fraction present in the product obtained by catalytic cracking. By the complete gasoline fraction is meant the C4+-fraction with such a boiling range that 98 ow of the gasoline is recovered at a temperature between 180 and 250 C. Measure 3 leads to such an improvement of the stability that metal silicates belonging to class II, which as such have insufficient stability, are now suitable for use. Measure 3 is also suitable for metal silicates belonging to class I. These metal silicates show sufficient stability in themselves, but the use of measure 3 adds still considerably to their stability. If desired, measure 3 can be cabined with measure l and/or measure
2, which, in addition to enhancement of stability, results in considerable enhancement of selectivity.
L66~
The present patent application relates to the application of measure 3, combined with muzzler 2, if desired, when metal silicates belonging to classes I and II are used.
In the application of measure 3 it is not the complete gasoline fraction present in the product obtained by catalytic cracking that is subjected to upgrading, but only a mixture of a light and a middle fraction, which mixture is separated from the cracked product by distillation. In order to achieve the desired stability improvement of the crystalline metal silicates belonging to classes I and II the separation between the mixture of the light and the middle fraction on the one hand and the heavy fraction on the other should be carried out in such a way that the heavy fraction has an aromatics content which is related to the aromatics content of the complete gasoline fraction present in the cracked product according to a given relation. If the aromatics content of the complete gasoline fraction present in the cracked product is a ow and this gasoline fraction is considered to consist of a light, a middle and a heavy fraction, the distillation should be carried out in such a way that the heavy fraction has such an aromatics content of b ow as to satisfy the relation 0-35 ' b ' 0 45 the present patent application relates to a process for upgrading a gasoline produced by catalytic cracking, in which the starting material is a product obtained by catalytic cracking containing a complete gasoline fraction having an aromatics content of a ow, which gasoline fraction consists of a light, a middle and a heavy fraction, the heavy fraction having an aromatics content of b ow and 0-35 be < 0.45, in which the mixture of the light and middle fraction, is separated by 3Q distillation from the product obtained by catalytic cracking, and in which this mixture, or a part of it, is contacted with a crystalline metal silicate belonging to classes I and II.
23::~6~L
According to a first embodiment the complete above-mentioned mixture of the light and middle fraction is subjected to upgrading, in which, owing to the use of measure 3, the stability of the silicates belonging to classes I and II is seen to improve considerably. According to a second preferred embodiment, a combination of measure 3 with the above-mentioned measure 2, leads not only to improvement of the stability, but also to improvement of the selectivity of the silicates belonging to classes I and II.
In the second embodiment according to the present patent apply-cation in which measure 3 is combined with measure 2, it is not the mixture of the light and heavy fraction that is subjected to upgrading, but only the middle fraction. In order to achieve the desired selectivity improvement of the silicates belonging to classes I and II the separation of the light from the middle fraction should be carried out in such a way that a middle fraction is obtained having such an aromatics content of c ow as to satisfy the relation 0.30 ' ad ' 0.80, in which d represents the aromatics content of the mixture of the light and middle fraction. Therefore, the middle fraction is preferably separated from the mixture of the light and middle fraction such that 0.30 < ad ' 0.80 and is contacted with the crystalline metal silicate.
In the present process the starting material is a gasoline obtained by catalytic cracking. Such gasolines may very suitably be prepared by applying catalytic cracking to heavy hydrocarbon oils such as atmospheric gas oils, vacuum gas oils, disaffiliated distillation residues and mixtures thereof. Preference is given to the use of a gas oil as feed. Catalytic cracking on a commercial scale is generally carried out in a continuous process using an arrangement which substantially consists of a vertically disposed cracking reactor and a catalyst regenerator. Hot regenerated catalyst leaving the regenerator is suspended in the oil to be ~23~66 cracked and then the mixture is passed through the cracking reactor m upward direction. m e deactivated catalyst is sop æ axed from the cracked product, stripped and transferred to the regenerator. m e cracked product is separated to form a light fraction having a high content of C3 and C4 olefins, a gasoline fraction and several heavy fractions such as a light cycle oil, a middle cycle oil, a heavy cycle oil and slurry oil.
The crystalline metal silicate which in the present process is used as catalyst should have a Sophie + AYE) molar ratio higher than 10, a Sophie molar ratio lower than 250 and/or a Sue mylar ratio lower than 500.
When a crystalline iron silicate belonging to class I is used, preference is given to the use of a silicate having a Sophie molt ratio higher than 25, but lower than 250 and in particular of 50-175~ When a crystalline iron/alumlnium silicate belonging to class I is used, preference is given to the use of a silicate having a Sophie mow æ ratio higher than 25, but fewer than 250 and in particle æ of 50-175 and a Sue mow æ ratio of at least 500, but lower than 1200 and in p æ tickle æ of at least 500, but lower than 800. When a crystalline aluminum silicate belonging to class II it used, preference is given to the use of a silicate having a Sue molt ratio higher than 25, but lower than 500 and in particle of 50-400. When a crystalline iron/aluminium silicate belonging to class II is used, preference is given to the use of a silicate having a Sue molar ratio higher than 25, but lower than 500 and in p æ tickle æ of 50-400 and a Sophie molar ratio higher than 25 and in particle æ
higher than 100. The crystalline silicates æ e defined among the other things by the X-ray powder diffraction pattern which they skew after one hour's calcination in air at 500 C. In this pattern the strongest lines should be the four lines mentioned in Table A. The complete X-ray powder diffraction pattern of a typical example of the present crystalline silicates after one hour's calcination in air a S00 C is given in Table B.
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TABLE B
do) Rot. into do Rot. in.
11.1 100 3.84 (D) 57 10.0 (D) 70 3.72 (D) 31 8.93 1 3.63 16 7.99 1 3.47 < 1 7.42 2 3.43 5 6.68 7 3.34 2 6.35 11 3.30 5 5.97 17 3.25 5.70 7 3.05 8 5.56 lo 2.98 11 5.35 2 2.96 3 4.98 (D) 6 2.86 2 4.60 4 2.73 2 4.35 5 2.60 ?
4.25 7 2.48 3 4.07 2 2.40 2 _ (~) = doublet The crystalline silicates can be prepared starting from an aqueous mixture comprising the following cc~pounds: one or more silicon compounds, one or more compounds which contain a monovalent organic cation (R) or from which such a cation is S formed during the preparation of the silicate, one or more compounds in which iron is present in a trivalent form and/or one or more aluminum compounds, and one or more compounds of an alkali metal (M). The preparation is carried out by keeping the mixture at an elevated temperature until the silicate has formed, and subsequently separating the silicate crystals from the mother liquor and washing, drying and calcining the crystals. In the aqueous mixture from which the silicates are prepared the various I
compounds should be present in the following ratios, expressed in moles of the oxides:
MOO : Sue < 0.35, Rho : Sue = Oily - 0.5, Sue : (Foe + Allah) > lo end HO : Sue = 5 - lo.
If in the preparation of the crystalline silicates the starting material is an aqueous mixture in which one or more alkali metal compounds are present, the crystalline silicates obtained will contain alkali metal. Depending on the concentration of alkali metal ccmp~unds in the aqueous mixture the crystalline silicates obtained may contain more than 1 ow alkali metal. Since the presence of alkali metal in the crystalline silicates has an unfavorable influence on their catalytic properties, it is common practice in the case of crystalline silicates with a relatively high alkali metal content to reduce this content before using these silicates as catalysts. A reduction of the alkali metal content to less than 0.05 ow is usually sufficient to this end.
The reduction of the alkali metal content of crystalline silicates can very suitably be effected by treating the silicates ones or several times with a solution of an ammonium compound. During this treatment alkali metal ions are exchanged for Ho ions and the silicate is converted to the NO form. The NH4 form of the silicate is converted to the H+ form by calcination. The formula of the calcined metal silicate, expressed in moles of oxides, is lo 0.3)x2o.aFe2o3.bAl2o3.csio2~ in which X = alkali metal or hydrogen, a > 0, b > 0, a + b = l, c > lo In the present process the mixture of light and middle fraction, or preferably the middle fraction is subjected to the catalytic treatment Preferably the treated product is mixed with the untreated heavy fraction or light and heavy fractions, respectively, so that once again a complete gasoline fraction is I obtained. The great advantage of such a process over a process in which the cc~plete gasoline fraction is subjected to upgrading is 66~
g that in the former process a much smaller plant will suffice.
If in the present process use is made of the preferred ~nbodlment, which comprises combination of measure 3 with measure 2, the separation of the light from the middle fraction is carried S out in such a way that the middle fraction has an aromatics content of c ow and the relation 0.30 c d < 0.80, is satisfied.
Preferably the separation is carried out in such a way that the middle fraction has an aromatics content of c ow and the relation 0.35 < d < 0.70, is satisfied.
The application of measure 2 results in a considerable enhancement of the selectivity of the present metal silicates when these silicates are used as catalysts for upgrading a gasoline obtained by catalytic cracking. This selectivity enhancement occurs both when silicates belonging to class I are used and when silicates belonging to class II are used.
Measure l comprises the application of the metal silicates as a mixture with a zinc-containing composition which, in addition to zinc, contains at least one metal chosen from the group consisting of chromium and aluminum and which composition has been prepared starting from at least one precipitate obtained by adding a basic reacting substance to one or more aqueous solutions containing salts of the metals involved.
An investigation into this subject has shown that enhancement of the selectivity of the silicates belonging to classes I and II, such as it occurs with the second embodiment of the present process when measure 3 is used in combination with measure 2, can also be achieved by using measure 3 in combination with measure l.
It has further been found that the selectivity of the silicates belonging to classes I and II, which can be considerably enhanced by using measure 3 in combination with measure 2, can be enhanced much further yet by applying measure l in addition. Therefore, in the process of the present patent application both when using measure 3 and when using measure 3 in combination with measure 2, ~3~6~L
the catalyst used by preference is a mixture of a silicate belonging to class I or II with a zinc-contaLning composition as described herein before. The zinc-containing composition used is preferably a composition which, in addition to zinc, comprises chromium and m which the atomic percentage of zinc calculated on the sum of zinc and chromium is 60-80%, and the ratio of ingredients is preferably chosen such that per part by weight silicate the mixture contains 0.1-12.5, and in p æ titular 0.5:8, parts by weight metal oxides coming from the precipitate.
The present process can very suitably be carried out by passing the feed in upward or dcwnw æ d direction through a vertically disposed reactor containing a fixed or moving bed of the catalyst mixture. Suitable conditions for carrying out the process are a temperature of 300-600 C, a pressure of 1-50 bar and a space velocity of 0.1-10 kg.kg oh 1. m e process is preferably carried out under the following conditions: a temperature of 400-500 C, a pressure of 2.5-25 bar and a space velocity of 0.2-3 kg.kg oh 1. The process may be carried out in the presence of hydrogen, if desired.
m e invention is now illustrated by the following example.
EYE
aeration of Catalysts 1 and 2 An aluminum silicate (Silicate 1) and an iron/aluminium silicate (Silicate 2) were prepared by heating mixtures of sodium hydroxide, tetrapropylammonium hydroxide, amorphous silica and either sodium acuminate (for preparing Silicate 1), or sodium acuminate and ferris nitrate (for preparing Silicate 2) in water in an autoclave under autogenous pressure for 24 hours at 150 C.
After cooling of the reaction mixtures the silicates formed were filtered off, washed with water until the pi of the wash water was about 8 and dried at 120 C. After one hour's calcination in air at 500 C the silicates had the following properties:
I AL
a) an X-ray powder diffraction pattern substantially corresponding with that mentioned in Table B, b) a Sue l æ ratio of 330 for Silicate 1 and 600 for Silicate 2, and c) a Sophie far ratio of 130 for Silicate 2.
The metal silicates prepared in the above-described manner were boiled with a 1.0 molar ammonium nitrate solution, washed with waxer, toiled again with a 1.0 molar ammonium nitrate solution, washed and dried at 120 C. Catalysts 1 and 2 were lo prepared by pressing and grinding the dried materials to have a particle size of 0.4 mm and calcining the ground material at 500 C.
Preparation of Catalyst 3 Such quantities of Zn(NO3)2.6 a and Crown a were dissolved in water as to produce a solution in which the Zn/(Zn + Or) atomic ratio was 0.67. m is solution, together with a stoichiometric quantity of a 10% aqueous NH3 solution, was pumped with stirring through a mixing unit which was kept at a temperature of 20 C. The Zn/Cr co-precipitate obtained was collected and left to age for one hour with stirring at 20 C. The solid material was filtered off, washed with water until the wash water was free of NO ions and dried at 120 C. Catalyst 3 was prepared by pressing and grinding the dried material to have a particle size of 0.4 mm, and calcining the ground material at 400 C.
Preparation of Catalyst 4 This catalyst was prepared by mixing Catalysts 1 and 3 in a weight ratio 1:5.
Catalysts 1, 2 and 4 were tested in seven experiments (Experiments 1-7) for enhancing the qua try of six gasolines obtained by catalytic cracking (Gasolines A-F). Gasolines A and B
constituted the complete gasoline fractions present in the cracked products from which they had been separated. Gasoline A had a RDN-O Ares Of ah octane number without addition of lead) of 92.3 : .-'~3~6~
and Gasoline B had a RON-O of 85.4. Gasoline C was obtained as thy mixture of the light and middle fraction when separating Gasoline B by distillation to form on the one hand a mixture of a light and a middle fraction and on the other hand a heavy fraction. Gasoline D was obtained as the middle fraction when separating Gasoline C
by distillation of form a light and a middle fraction. Guzzle me E
was obta mod as the middle fraction when separating Gasoline A by distillation to form on the one hand a mixture of a light and a middle fraction and on the other hand a heavy fraction, followed by separation of the mixture of the light and middle fraction by distillation to form a light and a middle fraction. Gasoline F was obtained as the mixture of the light and middle fraction when separating Gasoline B by distillation to form on the one hand a mixture of a light and a middle fraction and on the other hand a heavy fraction m e aromatics contents of Gasolines A-E as well as the aromatics content of a number of fractions obtained in the preparation of Gasolines C-F are given in Table C. The letters a, b, c and d used in the table refer to the aromatics contents of the complete gasoline fraction, the heavy fraction the middle fraction and the mixture of the light and middle fraction, respectively. m e experiments were carried out in a reactor containing a fixed catalyst bed. In all the experiments were used a temperature of 450 C and a pressure of 5 bar. The space velocities used in the experiments (calculated on the quantities of silicate present in the catalysts) and the results of the experiments are listed in Table D.
When the term "total product" is used in Table D, it refers for the experiments in which Gasoline fractions C and F were used as starting material to the mixture of the untreated heavy fraction and the product obtained in the catalytic treatment of the mixture of the light and middle fraction, and for the experiments in which Gasoline fractions D and E were used as starting material, to the mixture of the untreated light and heavy fraction and the product obtained in the catalytic treatment of the middle fraction.
~3~66~
The values given in Table D for ~C5 / QRDN-O (loss of C5 hydrocarbons per point go mod in RON/O) represent a criterion of selectivity. According as the QC5 Jo RQN-O is lower, the catalyst has better selectivity.
The values given in Table D for the rates of catalyst deactivation are a criterion of stability. The rate of catalyst deactivation is defined as the average reduction of catalyst activity per hour measured over the first 100 run hours. In this connection catalyst activity is understood to be:
lo (ow C5+ non-arcmatics in food C5+ non-aromatics in product) x 100 ow C5+ non-arcmatics in feed According as the rate of catalyst deactivation is lower, the catalyst has better stability.
TABLE C
_ ¦ Distillation Gasoline Aromatics content, ow temperature, C
_ 10 ow 98 ow a b c recovery recovery . __ A 24.2 9 228 _ .
B 27.0 23 226 _ . _ _ C 66.0 11.8 20 164 _ __ D l 26.2 90 163 E 62.1 23.211.6 87 158 _ _ F l 44.8 i _ 84 112 ~L~3~L~i6~
TABLE D
Experiment No. 1 2 3 4 5 6 7 _ _ _ _ Catalyst No. 2 2 2 1 1 4 2 -Space velocity 0.5 0.5 0.5 0.50.5 3.0 0.5 g go h-1 Feed gasoline B C D A E E F
DUO of total product 97.0 96.5 95.2 94.5 95.0 94.8 90.7 _ ~C5 /~RDN-O, ow 2.1 2.0 1.4 6.0 3.3 2.3 3.0 Rate of catalyst deactivation, h 1 0.45 0.180.21 0.90 0.50 0.52 0.17 .
RHO 11.6 11.1 9.8 2.2 2.7 2.5 5.3 66~L
Of the experiments mentioned in Table D only Experiments 2, 3, 5 and 6 are experiments according to the invention. In Experiment 2 use was made of measure 3 mentioned in the present patent application (application of the silicate to a mixture of a light and middle fraction with the relation 0 35 ' b < 0 45 being satisfied).
In Experiments 3, 5 and 6 the combination of measures 3 and 2 mentioned in the present patent application (application of the silicate to a middle fraction with the relations 0 35 b ' 0 45 and 0.30 < c 0.80 briny satisfied). In Experiment 6 measure 1 mentioned in the present patent application (application of the silicate mixed with a zinc-coNtaining composition) was used in addition. Experiments 1, 4 and 7 fall outside the scope of the invention. They have been included in the patent application for comparison. In Experiments 1, 4 and 7 measure 3 was not used. In Experiments 1 and 4 a complete gasoline fraction was used; in Experiment 7 a mixture of a light and a middle fraction was used, but the heavy fraction separated during the preparation of the mixture had too low an aromatics content.
On the experiments mentioned in Table D the following may be observed. Comparison of the results of Experiments 1 and 2 shows that using measure 3 results in considerable enhancement of the stability. The use of measure 3 has no influence on selectivity.
Comparison of the results of Experiments 1 and 3, like comparison of the results of Experiments 4 and 5, shows that by the use of a combination of measures 3 and 2 both stability and selectivity are enhanced considerably. Comparison of the results of Experiments 5 and 6 shows that by using measure 1 in addition to measures 3 and 2 there can be achieved further enhancement of selectivity.
Comparison of the results of Experiments 1 and 7 shows that the separation such as it was carried out for the preparation of Gasoline F leads to reduction of selectivity and to an us-acceptably few RON.
L66~
The present patent application relates to the application of measure 3, combined with muzzler 2, if desired, when metal silicates belonging to classes I and II are used.
In the application of measure 3 it is not the complete gasoline fraction present in the product obtained by catalytic cracking that is subjected to upgrading, but only a mixture of a light and a middle fraction, which mixture is separated from the cracked product by distillation. In order to achieve the desired stability improvement of the crystalline metal silicates belonging to classes I and II the separation between the mixture of the light and the middle fraction on the one hand and the heavy fraction on the other should be carried out in such a way that the heavy fraction has an aromatics content which is related to the aromatics content of the complete gasoline fraction present in the cracked product according to a given relation. If the aromatics content of the complete gasoline fraction present in the cracked product is a ow and this gasoline fraction is considered to consist of a light, a middle and a heavy fraction, the distillation should be carried out in such a way that the heavy fraction has such an aromatics content of b ow as to satisfy the relation 0-35 ' b ' 0 45 the present patent application relates to a process for upgrading a gasoline produced by catalytic cracking, in which the starting material is a product obtained by catalytic cracking containing a complete gasoline fraction having an aromatics content of a ow, which gasoline fraction consists of a light, a middle and a heavy fraction, the heavy fraction having an aromatics content of b ow and 0-35 be < 0.45, in which the mixture of the light and middle fraction, is separated by 3Q distillation from the product obtained by catalytic cracking, and in which this mixture, or a part of it, is contacted with a crystalline metal silicate belonging to classes I and II.
23::~6~L
According to a first embodiment the complete above-mentioned mixture of the light and middle fraction is subjected to upgrading, in which, owing to the use of measure 3, the stability of the silicates belonging to classes I and II is seen to improve considerably. According to a second preferred embodiment, a combination of measure 3 with the above-mentioned measure 2, leads not only to improvement of the stability, but also to improvement of the selectivity of the silicates belonging to classes I and II.
In the second embodiment according to the present patent apply-cation in which measure 3 is combined with measure 2, it is not the mixture of the light and heavy fraction that is subjected to upgrading, but only the middle fraction. In order to achieve the desired selectivity improvement of the silicates belonging to classes I and II the separation of the light from the middle fraction should be carried out in such a way that a middle fraction is obtained having such an aromatics content of c ow as to satisfy the relation 0.30 ' ad ' 0.80, in which d represents the aromatics content of the mixture of the light and middle fraction. Therefore, the middle fraction is preferably separated from the mixture of the light and middle fraction such that 0.30 < ad ' 0.80 and is contacted with the crystalline metal silicate.
In the present process the starting material is a gasoline obtained by catalytic cracking. Such gasolines may very suitably be prepared by applying catalytic cracking to heavy hydrocarbon oils such as atmospheric gas oils, vacuum gas oils, disaffiliated distillation residues and mixtures thereof. Preference is given to the use of a gas oil as feed. Catalytic cracking on a commercial scale is generally carried out in a continuous process using an arrangement which substantially consists of a vertically disposed cracking reactor and a catalyst regenerator. Hot regenerated catalyst leaving the regenerator is suspended in the oil to be ~23~66 cracked and then the mixture is passed through the cracking reactor m upward direction. m e deactivated catalyst is sop æ axed from the cracked product, stripped and transferred to the regenerator. m e cracked product is separated to form a light fraction having a high content of C3 and C4 olefins, a gasoline fraction and several heavy fractions such as a light cycle oil, a middle cycle oil, a heavy cycle oil and slurry oil.
The crystalline metal silicate which in the present process is used as catalyst should have a Sophie + AYE) molar ratio higher than 10, a Sophie molar ratio lower than 250 and/or a Sue mylar ratio lower than 500.
When a crystalline iron silicate belonging to class I is used, preference is given to the use of a silicate having a Sophie molt ratio higher than 25, but lower than 250 and in particular of 50-175~ When a crystalline iron/alumlnium silicate belonging to class I is used, preference is given to the use of a silicate having a Sophie mow æ ratio higher than 25, but fewer than 250 and in particle æ of 50-175 and a Sue mow æ ratio of at least 500, but lower than 1200 and in p æ tickle æ of at least 500, but lower than 800. When a crystalline aluminum silicate belonging to class II it used, preference is given to the use of a silicate having a Sue molt ratio higher than 25, but lower than 500 and in particle of 50-400. When a crystalline iron/aluminium silicate belonging to class II is used, preference is given to the use of a silicate having a Sue molar ratio higher than 25, but lower than 500 and in p æ tickle æ of 50-400 and a Sophie molar ratio higher than 25 and in particle æ
higher than 100. The crystalline silicates æ e defined among the other things by the X-ray powder diffraction pattern which they skew after one hour's calcination in air at 500 C. In this pattern the strongest lines should be the four lines mentioned in Table A. The complete X-ray powder diffraction pattern of a typical example of the present crystalline silicates after one hour's calcination in air a S00 C is given in Table B.
~3~6~
TABLE B
do) Rot. into do Rot. in.
11.1 100 3.84 (D) 57 10.0 (D) 70 3.72 (D) 31 8.93 1 3.63 16 7.99 1 3.47 < 1 7.42 2 3.43 5 6.68 7 3.34 2 6.35 11 3.30 5 5.97 17 3.25 5.70 7 3.05 8 5.56 lo 2.98 11 5.35 2 2.96 3 4.98 (D) 6 2.86 2 4.60 4 2.73 2 4.35 5 2.60 ?
4.25 7 2.48 3 4.07 2 2.40 2 _ (~) = doublet The crystalline silicates can be prepared starting from an aqueous mixture comprising the following cc~pounds: one or more silicon compounds, one or more compounds which contain a monovalent organic cation (R) or from which such a cation is S formed during the preparation of the silicate, one or more compounds in which iron is present in a trivalent form and/or one or more aluminum compounds, and one or more compounds of an alkali metal (M). The preparation is carried out by keeping the mixture at an elevated temperature until the silicate has formed, and subsequently separating the silicate crystals from the mother liquor and washing, drying and calcining the crystals. In the aqueous mixture from which the silicates are prepared the various I
compounds should be present in the following ratios, expressed in moles of the oxides:
MOO : Sue < 0.35, Rho : Sue = Oily - 0.5, Sue : (Foe + Allah) > lo end HO : Sue = 5 - lo.
If in the preparation of the crystalline silicates the starting material is an aqueous mixture in which one or more alkali metal compounds are present, the crystalline silicates obtained will contain alkali metal. Depending on the concentration of alkali metal ccmp~unds in the aqueous mixture the crystalline silicates obtained may contain more than 1 ow alkali metal. Since the presence of alkali metal in the crystalline silicates has an unfavorable influence on their catalytic properties, it is common practice in the case of crystalline silicates with a relatively high alkali metal content to reduce this content before using these silicates as catalysts. A reduction of the alkali metal content to less than 0.05 ow is usually sufficient to this end.
The reduction of the alkali metal content of crystalline silicates can very suitably be effected by treating the silicates ones or several times with a solution of an ammonium compound. During this treatment alkali metal ions are exchanged for Ho ions and the silicate is converted to the NO form. The NH4 form of the silicate is converted to the H+ form by calcination. The formula of the calcined metal silicate, expressed in moles of oxides, is lo 0.3)x2o.aFe2o3.bAl2o3.csio2~ in which X = alkali metal or hydrogen, a > 0, b > 0, a + b = l, c > lo In the present process the mixture of light and middle fraction, or preferably the middle fraction is subjected to the catalytic treatment Preferably the treated product is mixed with the untreated heavy fraction or light and heavy fractions, respectively, so that once again a complete gasoline fraction is I obtained. The great advantage of such a process over a process in which the cc~plete gasoline fraction is subjected to upgrading is 66~
g that in the former process a much smaller plant will suffice.
If in the present process use is made of the preferred ~nbodlment, which comprises combination of measure 3 with measure 2, the separation of the light from the middle fraction is carried S out in such a way that the middle fraction has an aromatics content of c ow and the relation 0.30 c d < 0.80, is satisfied.
Preferably the separation is carried out in such a way that the middle fraction has an aromatics content of c ow and the relation 0.35 < d < 0.70, is satisfied.
The application of measure 2 results in a considerable enhancement of the selectivity of the present metal silicates when these silicates are used as catalysts for upgrading a gasoline obtained by catalytic cracking. This selectivity enhancement occurs both when silicates belonging to class I are used and when silicates belonging to class II are used.
Measure l comprises the application of the metal silicates as a mixture with a zinc-containing composition which, in addition to zinc, contains at least one metal chosen from the group consisting of chromium and aluminum and which composition has been prepared starting from at least one precipitate obtained by adding a basic reacting substance to one or more aqueous solutions containing salts of the metals involved.
An investigation into this subject has shown that enhancement of the selectivity of the silicates belonging to classes I and II, such as it occurs with the second embodiment of the present process when measure 3 is used in combination with measure 2, can also be achieved by using measure 3 in combination with measure l.
It has further been found that the selectivity of the silicates belonging to classes I and II, which can be considerably enhanced by using measure 3 in combination with measure 2, can be enhanced much further yet by applying measure l in addition. Therefore, in the process of the present patent application both when using measure 3 and when using measure 3 in combination with measure 2, ~3~6~L
the catalyst used by preference is a mixture of a silicate belonging to class I or II with a zinc-contaLning composition as described herein before. The zinc-containing composition used is preferably a composition which, in addition to zinc, comprises chromium and m which the atomic percentage of zinc calculated on the sum of zinc and chromium is 60-80%, and the ratio of ingredients is preferably chosen such that per part by weight silicate the mixture contains 0.1-12.5, and in p æ titular 0.5:8, parts by weight metal oxides coming from the precipitate.
The present process can very suitably be carried out by passing the feed in upward or dcwnw æ d direction through a vertically disposed reactor containing a fixed or moving bed of the catalyst mixture. Suitable conditions for carrying out the process are a temperature of 300-600 C, a pressure of 1-50 bar and a space velocity of 0.1-10 kg.kg oh 1. m e process is preferably carried out under the following conditions: a temperature of 400-500 C, a pressure of 2.5-25 bar and a space velocity of 0.2-3 kg.kg oh 1. The process may be carried out in the presence of hydrogen, if desired.
m e invention is now illustrated by the following example.
EYE
aeration of Catalysts 1 and 2 An aluminum silicate (Silicate 1) and an iron/aluminium silicate (Silicate 2) were prepared by heating mixtures of sodium hydroxide, tetrapropylammonium hydroxide, amorphous silica and either sodium acuminate (for preparing Silicate 1), or sodium acuminate and ferris nitrate (for preparing Silicate 2) in water in an autoclave under autogenous pressure for 24 hours at 150 C.
After cooling of the reaction mixtures the silicates formed were filtered off, washed with water until the pi of the wash water was about 8 and dried at 120 C. After one hour's calcination in air at 500 C the silicates had the following properties:
I AL
a) an X-ray powder diffraction pattern substantially corresponding with that mentioned in Table B, b) a Sue l æ ratio of 330 for Silicate 1 and 600 for Silicate 2, and c) a Sophie far ratio of 130 for Silicate 2.
The metal silicates prepared in the above-described manner were boiled with a 1.0 molar ammonium nitrate solution, washed with waxer, toiled again with a 1.0 molar ammonium nitrate solution, washed and dried at 120 C. Catalysts 1 and 2 were lo prepared by pressing and grinding the dried materials to have a particle size of 0.4 mm and calcining the ground material at 500 C.
Preparation of Catalyst 3 Such quantities of Zn(NO3)2.6 a and Crown a were dissolved in water as to produce a solution in which the Zn/(Zn + Or) atomic ratio was 0.67. m is solution, together with a stoichiometric quantity of a 10% aqueous NH3 solution, was pumped with stirring through a mixing unit which was kept at a temperature of 20 C. The Zn/Cr co-precipitate obtained was collected and left to age for one hour with stirring at 20 C. The solid material was filtered off, washed with water until the wash water was free of NO ions and dried at 120 C. Catalyst 3 was prepared by pressing and grinding the dried material to have a particle size of 0.4 mm, and calcining the ground material at 400 C.
Preparation of Catalyst 4 This catalyst was prepared by mixing Catalysts 1 and 3 in a weight ratio 1:5.
Catalysts 1, 2 and 4 were tested in seven experiments (Experiments 1-7) for enhancing the qua try of six gasolines obtained by catalytic cracking (Gasolines A-F). Gasolines A and B
constituted the complete gasoline fractions present in the cracked products from which they had been separated. Gasoline A had a RDN-O Ares Of ah octane number without addition of lead) of 92.3 : .-'~3~6~
and Gasoline B had a RON-O of 85.4. Gasoline C was obtained as thy mixture of the light and middle fraction when separating Gasoline B by distillation to form on the one hand a mixture of a light and a middle fraction and on the other hand a heavy fraction. Gasoline D was obtained as the middle fraction when separating Gasoline C
by distillation of form a light and a middle fraction. Guzzle me E
was obta mod as the middle fraction when separating Gasoline A by distillation to form on the one hand a mixture of a light and a middle fraction and on the other hand a heavy fraction, followed by separation of the mixture of the light and middle fraction by distillation to form a light and a middle fraction. Gasoline F was obtained as the mixture of the light and middle fraction when separating Gasoline B by distillation to form on the one hand a mixture of a light and a middle fraction and on the other hand a heavy fraction m e aromatics contents of Gasolines A-E as well as the aromatics content of a number of fractions obtained in the preparation of Gasolines C-F are given in Table C. The letters a, b, c and d used in the table refer to the aromatics contents of the complete gasoline fraction, the heavy fraction the middle fraction and the mixture of the light and middle fraction, respectively. m e experiments were carried out in a reactor containing a fixed catalyst bed. In all the experiments were used a temperature of 450 C and a pressure of 5 bar. The space velocities used in the experiments (calculated on the quantities of silicate present in the catalysts) and the results of the experiments are listed in Table D.
When the term "total product" is used in Table D, it refers for the experiments in which Gasoline fractions C and F were used as starting material to the mixture of the untreated heavy fraction and the product obtained in the catalytic treatment of the mixture of the light and middle fraction, and for the experiments in which Gasoline fractions D and E were used as starting material, to the mixture of the untreated light and heavy fraction and the product obtained in the catalytic treatment of the middle fraction.
~3~66~
The values given in Table D for ~C5 / QRDN-O (loss of C5 hydrocarbons per point go mod in RON/O) represent a criterion of selectivity. According as the QC5 Jo RQN-O is lower, the catalyst has better selectivity.
The values given in Table D for the rates of catalyst deactivation are a criterion of stability. The rate of catalyst deactivation is defined as the average reduction of catalyst activity per hour measured over the first 100 run hours. In this connection catalyst activity is understood to be:
lo (ow C5+ non-arcmatics in food C5+ non-aromatics in product) x 100 ow C5+ non-arcmatics in feed According as the rate of catalyst deactivation is lower, the catalyst has better stability.
TABLE C
_ ¦ Distillation Gasoline Aromatics content, ow temperature, C
_ 10 ow 98 ow a b c recovery recovery . __ A 24.2 9 228 _ .
B 27.0 23 226 _ . _ _ C 66.0 11.8 20 164 _ __ D l 26.2 90 163 E 62.1 23.211.6 87 158 _ _ F l 44.8 i _ 84 112 ~L~3~L~i6~
TABLE D
Experiment No. 1 2 3 4 5 6 7 _ _ _ _ Catalyst No. 2 2 2 1 1 4 2 -Space velocity 0.5 0.5 0.5 0.50.5 3.0 0.5 g go h-1 Feed gasoline B C D A E E F
DUO of total product 97.0 96.5 95.2 94.5 95.0 94.8 90.7 _ ~C5 /~RDN-O, ow 2.1 2.0 1.4 6.0 3.3 2.3 3.0 Rate of catalyst deactivation, h 1 0.45 0.180.21 0.90 0.50 0.52 0.17 .
RHO 11.6 11.1 9.8 2.2 2.7 2.5 5.3 66~L
Of the experiments mentioned in Table D only Experiments 2, 3, 5 and 6 are experiments according to the invention. In Experiment 2 use was made of measure 3 mentioned in the present patent application (application of the silicate to a mixture of a light and middle fraction with the relation 0 35 ' b < 0 45 being satisfied).
In Experiments 3, 5 and 6 the combination of measures 3 and 2 mentioned in the present patent application (application of the silicate to a middle fraction with the relations 0 35 b ' 0 45 and 0.30 < c 0.80 briny satisfied). In Experiment 6 measure 1 mentioned in the present patent application (application of the silicate mixed with a zinc-coNtaining composition) was used in addition. Experiments 1, 4 and 7 fall outside the scope of the invention. They have been included in the patent application for comparison. In Experiments 1, 4 and 7 measure 3 was not used. In Experiments 1 and 4 a complete gasoline fraction was used; in Experiment 7 a mixture of a light and a middle fraction was used, but the heavy fraction separated during the preparation of the mixture had too low an aromatics content.
On the experiments mentioned in Table D the following may be observed. Comparison of the results of Experiments 1 and 2 shows that using measure 3 results in considerable enhancement of the stability. The use of measure 3 has no influence on selectivity.
Comparison of the results of Experiments 1 and 3, like comparison of the results of Experiments 4 and 5, shows that by the use of a combination of measures 3 and 2 both stability and selectivity are enhanced considerably. Comparison of the results of Experiments 5 and 6 shows that by using measure 1 in addition to measures 3 and 2 there can be achieved further enhancement of selectivity.
Comparison of the results of Experiments 1 and 7 shows that the separation such as it was carried out for the preparation of Gasoline F leads to reduction of selectivity and to an us-acceptably few RON.
Claims (11)
1. A process for upgrading a gasoline obtained by catalytic cracking, characterized in that the starting material is a product obtained by catalytic cracking containing a complete gasoline fraction having an aromatics content of a %w, which gasoline fraction consists of a light, a middle and a heavy fraction, the heavy fraction having an aromatics content of b %w and the mixture of the light and middle fraction having an aromatics content of d %w and 0.35 < ? < 0.45, that the mixture of the light and middle fraction, is separated by distillation from the product obtained by catalytic cracking and that this mixture or a part of it, is contacted with a crystalline metal silicate which after one hour's calcination in air at 500 °C has the following properties:
a) an X-ray powder diffraction pattern in which the strongest lines are the four lines mentioned in Table A, b) in the formula which expresses the composition of the silicate in moles of the oxides and which, in addition to SiO2, includes at least one member chosen from the group consisting of Fe203 and Al2O3 the SiO2/(Fe203 + Al203) molar ratio is higher than 10 while in an iron silicate or an iron-aluminium silicate the SiO2/Fe203 molar ratio is lower than 250 or in an aluminium silicate the SiO2/Al203 molar ratio is lower than 500.
a) an X-ray powder diffraction pattern in which the strongest lines are the four lines mentioned in Table A, b) in the formula which expresses the composition of the silicate in moles of the oxides and which, in addition to SiO2, includes at least one member chosen from the group consisting of Fe203 and Al2O3 the SiO2/(Fe203 + Al203) molar ratio is higher than 10 while in an iron silicate or an iron-aluminium silicate the SiO2/Fe203 molar ratio is lower than 250 or in an aluminium silicate the SiO2/Al203 molar ratio is lower than 500.
2. A process as claimed in claim 1, characterized in that the middle fraction is separated from the mixture of the light and middle fraction such that 0.30 < ? < 0.80, wherein c = aromatics content (%w) of the middle fraction and d = aromatics content (%w) of the mixture of the light and middle fraction, and that said middle fraction is contacted with the crystalline metal silicate.
3. A process as claimed in claim 1 or 2, characterized in that the metal silicate is an iron silicate having a SiO2/Fe2O3 molar ratio higher than 25,but lower than 250.
4. A process as claimed in claim 1 or 2, characterized in that the metal silicate is an iron/aluminium silicate having a SiO2/Fe203 molar ratio higher than 25, but lower than 250 and a SiO2/Al203 molar ratio of at least 500, but lower than 1200.
5. A process as claimed in claim 1 or 2, characterized in that the metal silicate is an aluminium silicate having a SiO2/Al203 molar ratio higher than 25, but lower than 500.
6. A process as claimed in claim 1 or 2, characterized in that the metal silicate is an iron/aluminium silicate having a SiO2/Al203 molar ratio higher than 25, but lower than 500 and a SiO2/Fe2O3 molar ratio higher than 25.
7. A process as claimed in claim 1 or 2, characterized in that the treated fraction is mixed with the untreated fraction(s).
8. A process as claimed in claim 1, characterized in that the fraction to be treated is contacted with a mixture of two catalysts, one of which is the metal silicate and the other a zinc-containing coposition which, in addition to zinc, comprises at least one metal chosen from the group consisting of chromium and aluminium and which composition has been prepared starting from at least one precipitate which has been obtained by adding a basic reacting substance to one or more aqueous solutions containing salts of the metals involved.
9. A process as claimed in claim 8, characterized in that the zinc containing composition in addition to zinc comprises chromium and that the atomic percentage of zinc calculated on the sum of zinc and chromium is 60-80%.
10. A process as claimed in claim 8 or 9, characterized in that per part by weight silicate the catalyst mixture contains 0.1-12.5 parts by weight metal oxides coming from the precipitate.
11. A process as claimed in claim 1 or 2, characterized in that it is carried out at a temperature of 300-600 °C, a pressure of 1-50 bar and a space velocity of 0.1-10 kg.kg-1.h-1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8302518 | 1983-07-14 | ||
| NL8302518A NL8302518A (en) | 1983-07-14 | 1983-07-14 | PROCESS FOR IMPROVING THE QUALITY OF GASOLINE. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1231661A true CA1231661A (en) | 1988-01-19 |
Family
ID=19842160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000454439A Expired CA1231661A (en) | 1983-07-14 | 1984-05-16 | Process for upgrading a gasoline |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS6038493A (en) |
| CA (1) | CA1231661A (en) |
| NL (1) | NL8302518A (en) |
| ZA (1) | ZA845383B (en) |
-
1983
- 1983-07-14 NL NL8302518A patent/NL8302518A/en not_active Application Discontinuation
-
1984
- 1984-05-16 CA CA000454439A patent/CA1231661A/en not_active Expired
- 1984-07-12 JP JP59143421A patent/JPS6038493A/en active Pending
- 1984-07-12 ZA ZA845383A patent/ZA845383B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NL8302518A (en) | 1985-02-01 |
| JPS6038493A (en) | 1985-02-28 |
| ZA845383B (en) | 1985-02-27 |
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