CA1203496A - Process for improving the quality of gasoline - Google Patents
Process for improving the quality of gasolineInfo
- Publication number
- CA1203496A CA1203496A CA000427430A CA427430A CA1203496A CA 1203496 A CA1203496 A CA 1203496A CA 000427430 A CA000427430 A CA 000427430A CA 427430 A CA427430 A CA 427430A CA 1203496 A CA1203496 A CA 1203496A
- Authority
- CA
- Canada
- Prior art keywords
- gasoline
- sio2
- olefins
- silicate
- fraction
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 23
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 23
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 23
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 23
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052914 metal silicate Inorganic materials 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000000634 powder X-ray diffraction Methods 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract 4
- 229910052593 corundum Inorganic materials 0.000 claims abstract 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract 2
- 150000001336 alkenes Chemical class 0.000 claims description 26
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical group O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 21
- 150000004760 silicates Chemical class 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000003921 oil Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001833 catalytic reforming Methods 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- -1 olefins Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/88—Ferrosilicates; Ferroaluminosilicates
-
- 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
- C10G35/065—Catalytic reforming characterised by the catalyst used containing crystalline zeolitic molecular sieves, other than aluminosilicates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A B S T R A C T
PROCESS FOR IMPROVING THE QUALITY OF GASOLINE
The quality of a gasoline obtained by catalytic cracking is improved by contacting the gasoline with a crystalline metal silicate which after one hour's calcination in air at 500°C, has the following properties:
a) thermally stable up to a temperature of at least 600°C, b) an X-ray powder diffraction pattern in which the strongest lines are the four lines mentioned in Table A.
PROCESS FOR IMPROVING THE QUALITY OF GASOLINE
The quality of a gasoline obtained by catalytic cracking is improved by contacting the gasoline with a crystalline metal silicate which after one hour's calcination in air at 500°C, has the following properties:
a) thermally stable up to a temperature of at least 600°C, b) an X-ray powder diffraction pattern in which the strongest lines are the four lines mentioned in Table A.
Description
~2~349~i PRO OESS FOR IMPROVTNG THE ~UALIIY OF G~SOLINE
The invention relates to a process for improving the quality of gasoline obtained by catalytic cracking.
Gasoline obtained by catalytic cracking has a high olefLns content. This is the reason why the gasoline displays a strong tendency to form gum. Gasoline obtained by catalytic cracking also has a relatively lcw aramatics content. This is the reason why the gasoline has a relatively low octane number. In view of the above-mentioned properties the quality of gasoline obtained by catalytic cracking must be improved, before it becomes eligible for use as tor gasoline. Such quality imprcvement may be carried out by catalytic reforming, in ~hich, among other things, the olefins content will fall and the aramatics content will rise. A serious drawback connected with the catalytic reforming of gasoline obtained by catalytic cracking is this gasoline's high content of sulphur ccmpounds and nitrogen co~pounds. Since the presence of sulphur and nitrogen campounds in the feed has a highly unfavourable effect Gn the performance of catalysts suitable for use in reforming, extreme remx~7al of said compounds from the feed is needed before the latter can be subjected to catalytic reforming. This requires a catalytic hydrotreatment under extra severe conditions. Plthough the abc~e-mentioned two-step process, in which gasoline is first subjected to a catalytic hydrotreatment under extra severe conditions and subsequently to catalytic reforming, results in a considerable quality improvement of the gasoline obtained by catalytic cracking, there is an urgent need for a prccess which-leads to the desired end in a single step.
Recently new crystalline metal silicates having a special structure have been synthesized, which silicates show catalytic '`~
, ~IL2()39L96 activity in the conversion of non-aramatic organic compounds, such as olefins, into aramatic hydrocarbons. me catalytic performance of these silicates is quite unsusceptible to the presence of sulphur and nitrogen campounds in the feed. m e crystalline metal silicates concerned are characterized in that after one hour's calc mation in air at 500C they have the following properties:
a) thermally stable up to a temperature of at least 600C, b) an X-ray powder diffraction pattern in which the strongest lines are the four lines mentioned in Table A.
TPBLE A
d~A) 11.1 ~ 0.2 10.0 + 0.2 3.84 + 0.07 3.72 + 0.06 c) in the formula which represents the composition of the silicate expressed in moles of the oxides and which, in addition to SiO2, includes either A12O3 or Fe2O3, the SiO2/A12O3 or the SiO2/Fe2O3, molar ratio is higher than 10.
In the present patent application a crystalline silicate having a thermal stability of at least tDC should be taken to be a silicate whose X-ray powder diffraction pattern, upon heating to a temperature of tC, remains substantially unchanged.
An investigation into the use of the above-mentioned crystalline iron or aluminium silicates as catalysts for improving the quality of gasoline obtained by catalytic cracking has shown that although same reducti~n in olefins content and same increase in aramatic content do occur, these changes are insufficient for the purpose of the desired quality improvement.
~2~ 9~i It has furhter been found that the catalysts have insufficient activity and stability. However, continued research has revealed that crystalline metal silicates having the special structure of the iron or aluminium silicates mentioned hereinbefore when used as catalysts for improving the quality o~ gasoline obtained by catalytic cracking, display excellent performance if they comprise both iron and aluminium and if, in addition, these metals are present in the silicate in such quantities that in the formula which represents the ccmposition of the silicate expressed in moles of the oxides, the SiO2/Fe2O3 molar ratlo is 25-90 and the SiO2/A1203 molar ratio is 250-1200.
Compared with the crystalline iron or aluminium silicates the above-mentioned iron-aluminium silicates have considerably better activity and stability and provide a gasoline having a considerably lower olefins content and a considerably higher octane number.
m e present patent application therefore relates to a process for improving the quality of gasoline obtained by catalytic cracking, in which the gasoline is contacted with a crystalline metal silicate which, after one hour's calcination in air at 500C has the properties mentioned above under a) and b) as well as the property that in the formula which represents the composition of the silicate expressed in moles of ~he oxides and which in addition to SiO2, includes both Fe203 and A12O3, the SiO2/Fe203 molar ratio is 25-90 and the SiO2/A1203 molar ratio is 250-1200.
In the process according to the invention the starting material is a gasoline obtained by catalytic cracking. Such gasolines may very suitably be prepared by the application of catalytic cracking to heavy hydrocarbon oils, such as atmos-pheric gas oils, vacuum gas oils, deasphalted vacuum residues and mixtures thereof. m e feed used by preference is a gas oil.
Catalytic cracking on a ccmmercial scale is usually carried out in a continuous process using an arrangement which consists 34~6 substantially of a vertically disposed cracklng reactor and a catalyst regenerator. Hot, regenerated catalyst coming from the regenerator is susp~nded in the oil to be cracked and the mixture is passed through the cracking reactor in an upward direction. The deactivated catalyst is separated from the cracked product and, following stripping, transported to the regenerator. m e cracked product is separated into 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 a slurYy oil.
The crystalline metal silicates used as catalysts in the process according to the invention are defined, am~ng other things, by the X-ray powder diffraction pattern which they show 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. m e cGmplete X-ray pcwder diffraction pattern of a typical example of a crystalline metal silicate used in the process according to the invention, is presented in Table B.
~L2~)34L~36 TABLE B
o o d(A)Rel. int. d(A) Rel. int.
______ _____.____ _____ _ ______~____ 11.1 1003.84 (D) 57 10.0(D) 703.72 (D) 31 8.93 13.63 16 7.99 13.47 7.42 23.43 5 6.68 73.34 2 6.35 ll 3.30 5 5.97 17 3.25 5.70 73.05 8 5.56 10 2.98 11 5.35 22.96 3 4.98 (D) 6 2.86 2 4.60 4 2.73 2 4.35 5 2.60 2 4.25 7 2.48 3 4.07 2 2.40 - ~ 2 4.00 4 _______________________ _ _________________________ __________ (D) = doublet m e crystalline metal silicates may be prepared starting from an aqueous mixture comprising the following cc~pounds: one or more compounds of an alkali metal (M), one or more organic nitrogen ccmpounds ~gN) which include an organic cation or from which an organic cation is formed d~ring the preparation of the silicate, one or more silicon compounds, one or more compounds cQmprising iron in a trivalent form and one or more alum m ium compounds.
m e preparation is carried out by maintaining the mlxture at an elevated temperature until the silicate has formed and ~3~9~i 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 compounds should be present in the following molar ratios, expressed - with the exception of the organic nitrogen compounds - in moles of the oxides:
M2O : SiO2 = 0.01-0-35, RN : SiO2 = 0.02-1.0, SiO2 : Fe2O3 = 25-270, SiO2 : A12O3 = 250-2400, and H2O SiO2 = 5-65-In the preparation of the silicates the base mixture started from may very suitably be a mixture which as a nitrogen compound comprises a quaternary alkylammonium compound, such as a tetrapropylammonium co~lpound. Preference is given to the use of an amine as an organic nitrogen compound and in particular to n-butylamine. Further, in the preparation of the silicates preference is given to the use of a base mixture which, as an alkali metal ccmpound comprises a sodium ccmpound and as a silicon ccmpound amorphous silica.
m e silicates prepared as described hereinbefore comprise alkali metal ions. By using suitable exchange methods these may be replaced by other cations, such as hydrogen ions or ammonium ions. m e crystalline silicates used in the process according to the invention preferably have an alkali metal content of less than 0.05 %w.
m e process according to the invention may very sui~ably be carried out by passing the feed in an upward or dcwnward direction through a vertically arranged reactor containing a fixed or a moving bed of the crystalline metal silicate.
Suitable conditions for carrying out the process according to the invention are a temperature of 300-600C, a pressure of 1-50 bar and a space velocity of 0.1-10 kg.kg l~h 1. The process is preferably carried out under the following conditions: a 39~916 te~erature of 400-500C, a pressure of 2.5-25 bar and a space velocity of 0.2-3 kg.kg 1.h 1 The process may be carried out in the presence of hydrogen, if desired.
In the process according to the invention the formation of aromatics is acccmpanied with cracking. As a result of this cracking the C4 product fraction contains a considerable proportion of C3 and C4 olefins. The investigation has revealed that the recirculation of the C4 product fraction leads to considerable improvement of the catalyst's selectivity and stability, whilst the excellent quality of the gasoline is maintained. Therefore, in the process according to the invention at least part of the C4 product fraction is preferably recirculated.
Depending upon the degrees of thoroughness with which the separation between the light fraction and the gasol me fraction of the catalytically cracked product is carried out, the separated gasoline may contain larger or smaller proportions of C3 and C4 olefins. The investigation has revealed that in the process according to the invention an increase in the C3 and/or C4 olefins content of the feed results in enhanced selectivity of the quality improvement. An increase in the C3 and/or C4 olefins content of the feed may be achieved in various ways. In the first place one may carry out the separation between the light fraction and the gasoline fraction f the cracked product less thoroughly and thus allow a considerable portion of the olefins usually present in the light fraction to go into the gasoline fraction. Another option is separating the gasoline from the catalytically cracked product and subsequently adding additional C3 and/or C4 olefins. For this purpose preference is given to the use of C3 and/or C4 olefins which can be separated from the light fraction of a product obtained by catalytic cracking. In view of its favourable effect on selectivity and quality improvement the process according to the invention is preferably applied to a ~3~96 gasoline obtained by catalytic cracking which has an increased C3 and/or C4 olefins content.
The invention is now elucidated with the aid of the following example.
EX~MPLE
Four crystalline silicates (silicates 1-4) were prepared by heating muxtures of NaOH, Fe(N03)3 and/or Na~102, amorphous silica containing 100 pp~w aluminium and C4HgNH2 or ~C3H7)4NOH
in water in an autoclave under autogenous pressure, with stirring, at 150C. In the preparation of silicates 1-3 the mixtures were heated for 24 hours. In the preparation of silicate 4 the mixture was heated for 120 hours. After cool mg of the reaction mixtures the silicates formed were filtered off, washed with water until the pH of the wash water was about 8 and dried at 120C. After one hour's calcination in air at 500C, silicates 1-4 had the following properties: -a3 thermally stable up to a temperature of at least 800C, b) an X-ray powder diffraction pattern substantially correspon-ding with that mentioned in Table B, and c) values of the SiO2/Fe2O3 and SiO2/A12O3 molar ratios as mentioned in Table C.
TABLE C
Silicate No. SiO2/Fe203 SiO2/A1203 _____________ _____________ ____________
The invention relates to a process for improving the quality of gasoline obtained by catalytic cracking.
Gasoline obtained by catalytic cracking has a high olefLns content. This is the reason why the gasoline displays a strong tendency to form gum. Gasoline obtained by catalytic cracking also has a relatively lcw aramatics content. This is the reason why the gasoline has a relatively low octane number. In view of the above-mentioned properties the quality of gasoline obtained by catalytic cracking must be improved, before it becomes eligible for use as tor gasoline. Such quality imprcvement may be carried out by catalytic reforming, in ~hich, among other things, the olefins content will fall and the aramatics content will rise. A serious drawback connected with the catalytic reforming of gasoline obtained by catalytic cracking is this gasoline's high content of sulphur ccmpounds and nitrogen co~pounds. Since the presence of sulphur and nitrogen campounds in the feed has a highly unfavourable effect Gn the performance of catalysts suitable for use in reforming, extreme remx~7al of said compounds from the feed is needed before the latter can be subjected to catalytic reforming. This requires a catalytic hydrotreatment under extra severe conditions. Plthough the abc~e-mentioned two-step process, in which gasoline is first subjected to a catalytic hydrotreatment under extra severe conditions and subsequently to catalytic reforming, results in a considerable quality improvement of the gasoline obtained by catalytic cracking, there is an urgent need for a prccess which-leads to the desired end in a single step.
Recently new crystalline metal silicates having a special structure have been synthesized, which silicates show catalytic '`~
, ~IL2()39L96 activity in the conversion of non-aramatic organic compounds, such as olefins, into aramatic hydrocarbons. me catalytic performance of these silicates is quite unsusceptible to the presence of sulphur and nitrogen campounds in the feed. m e crystalline metal silicates concerned are characterized in that after one hour's calc mation in air at 500C they have the following properties:
a) thermally stable up to a temperature of at least 600C, b) an X-ray powder diffraction pattern in which the strongest lines are the four lines mentioned in Table A.
TPBLE A
d~A) 11.1 ~ 0.2 10.0 + 0.2 3.84 + 0.07 3.72 + 0.06 c) in the formula which represents the composition of the silicate expressed in moles of the oxides and which, in addition to SiO2, includes either A12O3 or Fe2O3, the SiO2/A12O3 or the SiO2/Fe2O3, molar ratio is higher than 10.
In the present patent application a crystalline silicate having a thermal stability of at least tDC should be taken to be a silicate whose X-ray powder diffraction pattern, upon heating to a temperature of tC, remains substantially unchanged.
An investigation into the use of the above-mentioned crystalline iron or aluminium silicates as catalysts for improving the quality of gasoline obtained by catalytic cracking has shown that although same reducti~n in olefins content and same increase in aramatic content do occur, these changes are insufficient for the purpose of the desired quality improvement.
~2~ 9~i It has furhter been found that the catalysts have insufficient activity and stability. However, continued research has revealed that crystalline metal silicates having the special structure of the iron or aluminium silicates mentioned hereinbefore when used as catalysts for improving the quality o~ gasoline obtained by catalytic cracking, display excellent performance if they comprise both iron and aluminium and if, in addition, these metals are present in the silicate in such quantities that in the formula which represents the ccmposition of the silicate expressed in moles of the oxides, the SiO2/Fe2O3 molar ratlo is 25-90 and the SiO2/A1203 molar ratio is 250-1200.
Compared with the crystalline iron or aluminium silicates the above-mentioned iron-aluminium silicates have considerably better activity and stability and provide a gasoline having a considerably lower olefins content and a considerably higher octane number.
m e present patent application therefore relates to a process for improving the quality of gasoline obtained by catalytic cracking, in which the gasoline is contacted with a crystalline metal silicate which, after one hour's calcination in air at 500C has the properties mentioned above under a) and b) as well as the property that in the formula which represents the composition of the silicate expressed in moles of ~he oxides and which in addition to SiO2, includes both Fe203 and A12O3, the SiO2/Fe203 molar ratio is 25-90 and the SiO2/A1203 molar ratio is 250-1200.
In the process according to the invention the starting material is a gasoline obtained by catalytic cracking. Such gasolines may very suitably be prepared by the application of catalytic cracking to heavy hydrocarbon oils, such as atmos-pheric gas oils, vacuum gas oils, deasphalted vacuum residues and mixtures thereof. m e feed used by preference is a gas oil.
Catalytic cracking on a ccmmercial scale is usually carried out in a continuous process using an arrangement which consists 34~6 substantially of a vertically disposed cracklng reactor and a catalyst regenerator. Hot, regenerated catalyst coming from the regenerator is susp~nded in the oil to be cracked and the mixture is passed through the cracking reactor in an upward direction. The deactivated catalyst is separated from the cracked product and, following stripping, transported to the regenerator. m e cracked product is separated into 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 a slurYy oil.
The crystalline metal silicates used as catalysts in the process according to the invention are defined, am~ng other things, by the X-ray powder diffraction pattern which they show 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. m e cGmplete X-ray pcwder diffraction pattern of a typical example of a crystalline metal silicate used in the process according to the invention, is presented in Table B.
~L2~)34L~36 TABLE B
o o d(A)Rel. int. d(A) Rel. int.
______ _____.____ _____ _ ______~____ 11.1 1003.84 (D) 57 10.0(D) 703.72 (D) 31 8.93 13.63 16 7.99 13.47 7.42 23.43 5 6.68 73.34 2 6.35 ll 3.30 5 5.97 17 3.25 5.70 73.05 8 5.56 10 2.98 11 5.35 22.96 3 4.98 (D) 6 2.86 2 4.60 4 2.73 2 4.35 5 2.60 2 4.25 7 2.48 3 4.07 2 2.40 - ~ 2 4.00 4 _______________________ _ _________________________ __________ (D) = doublet m e crystalline metal silicates may be prepared starting from an aqueous mixture comprising the following cc~pounds: one or more compounds of an alkali metal (M), one or more organic nitrogen ccmpounds ~gN) which include an organic cation or from which an organic cation is formed d~ring the preparation of the silicate, one or more silicon compounds, one or more compounds cQmprising iron in a trivalent form and one or more alum m ium compounds.
m e preparation is carried out by maintaining the mlxture at an elevated temperature until the silicate has formed and ~3~9~i 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 compounds should be present in the following molar ratios, expressed - with the exception of the organic nitrogen compounds - in moles of the oxides:
M2O : SiO2 = 0.01-0-35, RN : SiO2 = 0.02-1.0, SiO2 : Fe2O3 = 25-270, SiO2 : A12O3 = 250-2400, and H2O SiO2 = 5-65-In the preparation of the silicates the base mixture started from may very suitably be a mixture which as a nitrogen compound comprises a quaternary alkylammonium compound, such as a tetrapropylammonium co~lpound. Preference is given to the use of an amine as an organic nitrogen compound and in particular to n-butylamine. Further, in the preparation of the silicates preference is given to the use of a base mixture which, as an alkali metal ccmpound comprises a sodium ccmpound and as a silicon ccmpound amorphous silica.
m e silicates prepared as described hereinbefore comprise alkali metal ions. By using suitable exchange methods these may be replaced by other cations, such as hydrogen ions or ammonium ions. m e crystalline silicates used in the process according to the invention preferably have an alkali metal content of less than 0.05 %w.
m e process according to the invention may very sui~ably be carried out by passing the feed in an upward or dcwnward direction through a vertically arranged reactor containing a fixed or a moving bed of the crystalline metal silicate.
Suitable conditions for carrying out the process according to the invention are a temperature of 300-600C, a pressure of 1-50 bar and a space velocity of 0.1-10 kg.kg l~h 1. The process is preferably carried out under the following conditions: a 39~916 te~erature of 400-500C, a pressure of 2.5-25 bar and a space velocity of 0.2-3 kg.kg 1.h 1 The process may be carried out in the presence of hydrogen, if desired.
In the process according to the invention the formation of aromatics is acccmpanied with cracking. As a result of this cracking the C4 product fraction contains a considerable proportion of C3 and C4 olefins. The investigation has revealed that the recirculation of the C4 product fraction leads to considerable improvement of the catalyst's selectivity and stability, whilst the excellent quality of the gasoline is maintained. Therefore, in the process according to the invention at least part of the C4 product fraction is preferably recirculated.
Depending upon the degrees of thoroughness with which the separation between the light fraction and the gasol me fraction of the catalytically cracked product is carried out, the separated gasoline may contain larger or smaller proportions of C3 and C4 olefins. The investigation has revealed that in the process according to the invention an increase in the C3 and/or C4 olefins content of the feed results in enhanced selectivity of the quality improvement. An increase in the C3 and/or C4 olefins content of the feed may be achieved in various ways. In the first place one may carry out the separation between the light fraction and the gasoline fraction f the cracked product less thoroughly and thus allow a considerable portion of the olefins usually present in the light fraction to go into the gasoline fraction. Another option is separating the gasoline from the catalytically cracked product and subsequently adding additional C3 and/or C4 olefins. For this purpose preference is given to the use of C3 and/or C4 olefins which can be separated from the light fraction of a product obtained by catalytic cracking. In view of its favourable effect on selectivity and quality improvement the process according to the invention is preferably applied to a ~3~96 gasoline obtained by catalytic cracking which has an increased C3 and/or C4 olefins content.
The invention is now elucidated with the aid of the following example.
EX~MPLE
Four crystalline silicates (silicates 1-4) were prepared by heating muxtures of NaOH, Fe(N03)3 and/or Na~102, amorphous silica containing 100 pp~w aluminium and C4HgNH2 or ~C3H7)4NOH
in water in an autoclave under autogenous pressure, with stirring, at 150C. In the preparation of silicates 1-3 the mixtures were heated for 24 hours. In the preparation of silicate 4 the mixture was heated for 120 hours. After cool mg of the reaction mixtures the silicates formed were filtered off, washed with water until the pH of the wash water was about 8 and dried at 120C. After one hour's calcination in air at 500C, silicates 1-4 had the following properties: -a3 thermally stable up to a temperature of at least 800C, b) an X-ray powder diffraction pattern substantially correspon-ding with that mentioned in Table B, and c) values of the SiO2/Fe2O3 and SiO2/A12O3 molar ratios as mentioned in Table C.
TABLE C
Silicate No. SiO2/Fe203 SiO2/A1203 _____________ _____________ ____________
2 108 1900
3 127 600
4 79 1000 The molar composition of the aqueous mixtures from which silicates 1-4 were prepared may be represented as follows:
v Na O w (C H7)4NOH ~ C4HgNH2 ~ A123 Z Fe23 2 2 25 where vl w, x, y and z have the values mentioned in Table D.
~2~3496 TABLE D
Silicate No. v w x y z _________ _ ___ ___ ___ ___ ___ 1 1 9 - 0.066 2 2.5 - 10 0.003 0.20 3 1 - 10 0.036 0.20 4 1 - 10 0.036 0.33 From silicates 1-4 were prepared silicates 5 8, respectively, by boiling silicates 1-4 with a 1.0 molar NH4NO3 solution, washing with water, boiling again with a 1.0 molar NH4NO3 solution, washing, drying at 120C and calcining at 500C.
Silicates 5-8 were tested in six experiments (Experiments 1-6) as catalysts for imprcving the quality of gasoline obtained by catalytic cracking. The experiments were ca~ried out in a reactor containing a fixed catalyst bed. All the experiments were carried out at a temperature of 450C, a pressure of 5 bar and a space velocity of 0.5 kg.kg l.h 1. In Experiments 5 and 6 the C4 product fraction was recirculated at a C4 /gasoline molar ratio of 10:1.
Experiments 1-5 were applied to a gasoline 1. Experiment 6 was applied to a gasoline 2 which had been obtained by mixing 93.0 pbw of gasoline 1 with 7O0 pbw of a mixture of butenes.
Gasoline 1 had the follow m g properties:
~3~9~i Composition in %w:
.____ _____________ .
C4 4.7 aromatics 24.2 naphthenes 13.6 5paraffins + olefins 57.5 olefins/paraffins weight ratio approx. 50/50 sulphur content, %w 0.14 nitrogen content, ppmw 60 final boiling point, C 244 10ozone number, le/g 4.0 MCN-O80.4 ___________________________________________________ The ozone number is a measure of the olefins content of the gasoline. According as the gasoline contains fewer olefins, the ozone number will be lcwer.
**
MON-O is the motor octane number without the addition of lead.
m e results of Experiments 1-6 are given in Tables E-G. me parameters activity, selectivity, stability and selectivity of the operation given in the Tables are defined as follows:
~)3~96 X X
.~ ~ .~
~ .~ ~
o ~ o h .U
o~
S ~ Y
~ R~
O _ .~ ~ ~
.~ ~ 1~ ~
~ 11 ~ ~ 11 ~'~U~ 3'- -~U~ ~
~i -- U~ _ H
34~
Selectivity of the operation =
increase in ~w aromatics decrease in %w C5+ fraction Of Experiment 1-6 only Experiments 4-6 are experiments according to the invention. Experiments 1-3 fall outside the scope of the invention. mey have been included in the patent application for comparison.
~3~6 TABLE E
Experiment No. - 1 2 3 4 Silicate No. - 5 6 7 8 Feed gasoline No.
Aromatics present in feed or total product, resp., ~w 24.2 36.8 41.0 43.3 46.7 C + present in feed or t~tal product, resp., ~w 95.3 79.8 82.0 79.8 74.9 Activity averaged over 350 hours, %w - 39.5 42.3 48.8 60.3 Selectivity averaged over 350 hours, %w - 44.8 55.8 55.2 52.5 Instability, %w - 65 38 39 33 MON-O of feed or liquid product, resp. 80.4 83.2 83.2 84.8 87.4 Ozone number of feed or liquid product, resp. mmole/g4.0 2.0 1.1 0.6 O.3 ~39L~6 TAB _ Experi~ent No. - 4 5 Silicate No. - 8 8 Feed gasoline No.
C4 recirculation - no yes Arcmatics present in feed or total product, resp., %w 24.2 46~.7 48.5 C + present in feed or total product, resp., ~w 95.3 74.9 77.1 Activity averaged over 350 hours, %w - 60.3 59.8 Selectivity averaged over 350 hours, %w - 52.5 57.2 Instability, %w - 33 27 MaN-O of feed or liquid product, resp. 80.4 87.4 87.3 Ozone number of feed or liquid product, resp. mmole/g 4.0 0.3 0.4 ~)3496 TABLE G
Experiment No. - 5 - 6 Silicate No. - 8 ~ 8 Feed gasoline No. 1 1 2 2 C4 recirculation - yes - yes Aromatics present in feed or total product, resp., %w 24.2 48.522.2 47.0 C present in feed or total product, resp., ~w 95.3 77.188.6 76.8 Increase of aromatics, ~w 24.3 24.8 Decrease of C5 , ~w 18.2 11.8 Selectivity of operation 1.3 2.1 ________________ ___________ _____________ .__________________ M~N-O of feed or total product, resp. 80.4 87.3 80.3 8702 Ozone number of fe~d or total product, resp. mmole/g 4.0 0.4 4.2 0.3 1~349 Ei Referring to the results mentioned in Tables E-G the following may be remarked.
Table E
Silicate 5 (aluminium silicate) is not suitable as catalyst for the present purpose, since this silicate has a very low average activity, a low average selectivity and a very low stability and, in addition, it provides a gasoline with a moderate octane nu~ber and a very high olefins content.
Silicate 6 (iron silicatet is not very suitable as catalyst for the present purpose, since this silicate has a very low average activity and, in addition provides a gasoline with a moderate octane number and a high olefins content.
Silicate 7 (iron-aluminium silicate, outside the scope of the invention) is not very suitable as catalyst for the present purpose, since this silicate has a low average activity and, in addition, provides a gasoline with a m~derate octane number and a relatively high olefins content.
Silicate 8 (iron-alu~inium silicate according to the invention) is excellently suitable as catalyst for the present purpose. m e silicate has a very high average activity, a high average selectivity and a very high stability. In addition, the silicate provides a gasoline with a very high octane ~umber and a very low olefins content.
Table F
Recirculation of the C4 product fraction results in a higher average selectivity and a higher stability whilst the very high average activity and very high product quality are maintained.
Table G
3o When a gasoline with a higher butenes content is used as the feed, then, at a comparable increase in arcmatics content, a much smaller loss of C5 is attained, in other words a higher selectivity of the quality improvement. Meanwhile the very high product quality is maintained.
v Na O w (C H7)4NOH ~ C4HgNH2 ~ A123 Z Fe23 2 2 25 where vl w, x, y and z have the values mentioned in Table D.
~2~3496 TABLE D
Silicate No. v w x y z _________ _ ___ ___ ___ ___ ___ 1 1 9 - 0.066 2 2.5 - 10 0.003 0.20 3 1 - 10 0.036 0.20 4 1 - 10 0.036 0.33 From silicates 1-4 were prepared silicates 5 8, respectively, by boiling silicates 1-4 with a 1.0 molar NH4NO3 solution, washing with water, boiling again with a 1.0 molar NH4NO3 solution, washing, drying at 120C and calcining at 500C.
Silicates 5-8 were tested in six experiments (Experiments 1-6) as catalysts for imprcving the quality of gasoline obtained by catalytic cracking. The experiments were ca~ried out in a reactor containing a fixed catalyst bed. All the experiments were carried out at a temperature of 450C, a pressure of 5 bar and a space velocity of 0.5 kg.kg l.h 1. In Experiments 5 and 6 the C4 product fraction was recirculated at a C4 /gasoline molar ratio of 10:1.
Experiments 1-5 were applied to a gasoline 1. Experiment 6 was applied to a gasoline 2 which had been obtained by mixing 93.0 pbw of gasoline 1 with 7O0 pbw of a mixture of butenes.
Gasoline 1 had the follow m g properties:
~3~9~i Composition in %w:
.____ _____________ .
C4 4.7 aromatics 24.2 naphthenes 13.6 5paraffins + olefins 57.5 olefins/paraffins weight ratio approx. 50/50 sulphur content, %w 0.14 nitrogen content, ppmw 60 final boiling point, C 244 10ozone number, le/g 4.0 MCN-O80.4 ___________________________________________________ The ozone number is a measure of the olefins content of the gasoline. According as the gasoline contains fewer olefins, the ozone number will be lcwer.
**
MON-O is the motor octane number without the addition of lead.
m e results of Experiments 1-6 are given in Tables E-G. me parameters activity, selectivity, stability and selectivity of the operation given in the Tables are defined as follows:
~)3~96 X X
.~ ~ .~
~ .~ ~
o ~ o h .U
o~
S ~ Y
~ R~
O _ .~ ~ ~
.~ ~ 1~ ~
~ 11 ~ ~ 11 ~'~U~ 3'- -~U~ ~
~i -- U~ _ H
34~
Selectivity of the operation =
increase in ~w aromatics decrease in %w C5+ fraction Of Experiment 1-6 only Experiments 4-6 are experiments according to the invention. Experiments 1-3 fall outside the scope of the invention. mey have been included in the patent application for comparison.
~3~6 TABLE E
Experiment No. - 1 2 3 4 Silicate No. - 5 6 7 8 Feed gasoline No.
Aromatics present in feed or total product, resp., ~w 24.2 36.8 41.0 43.3 46.7 C + present in feed or t~tal product, resp., ~w 95.3 79.8 82.0 79.8 74.9 Activity averaged over 350 hours, %w - 39.5 42.3 48.8 60.3 Selectivity averaged over 350 hours, %w - 44.8 55.8 55.2 52.5 Instability, %w - 65 38 39 33 MON-O of feed or liquid product, resp. 80.4 83.2 83.2 84.8 87.4 Ozone number of feed or liquid product, resp. mmole/g4.0 2.0 1.1 0.6 O.3 ~39L~6 TAB _ Experi~ent No. - 4 5 Silicate No. - 8 8 Feed gasoline No.
C4 recirculation - no yes Arcmatics present in feed or total product, resp., %w 24.2 46~.7 48.5 C + present in feed or total product, resp., ~w 95.3 74.9 77.1 Activity averaged over 350 hours, %w - 60.3 59.8 Selectivity averaged over 350 hours, %w - 52.5 57.2 Instability, %w - 33 27 MaN-O of feed or liquid product, resp. 80.4 87.4 87.3 Ozone number of feed or liquid product, resp. mmole/g 4.0 0.3 0.4 ~)3496 TABLE G
Experiment No. - 5 - 6 Silicate No. - 8 ~ 8 Feed gasoline No. 1 1 2 2 C4 recirculation - yes - yes Aromatics present in feed or total product, resp., %w 24.2 48.522.2 47.0 C present in feed or total product, resp., ~w 95.3 77.188.6 76.8 Increase of aromatics, ~w 24.3 24.8 Decrease of C5 , ~w 18.2 11.8 Selectivity of operation 1.3 2.1 ________________ ___________ _____________ .__________________ M~N-O of feed or total product, resp. 80.4 87.3 80.3 8702 Ozone number of fe~d or total product, resp. mmole/g 4.0 0.4 4.2 0.3 1~349 Ei Referring to the results mentioned in Tables E-G the following may be remarked.
Table E
Silicate 5 (aluminium silicate) is not suitable as catalyst for the present purpose, since this silicate has a very low average activity, a low average selectivity and a very low stability and, in addition, it provides a gasoline with a moderate octane nu~ber and a very high olefins content.
Silicate 6 (iron silicatet is not very suitable as catalyst for the present purpose, since this silicate has a very low average activity and, in addition provides a gasoline with a moderate octane number and a high olefins content.
Silicate 7 (iron-aluminium silicate, outside the scope of the invention) is not very suitable as catalyst for the present purpose, since this silicate has a low average activity and, in addition, provides a gasoline with a m~derate octane number and a relatively high olefins content.
Silicate 8 (iron-alu~inium silicate according to the invention) is excellently suitable as catalyst for the present purpose. m e silicate has a very high average activity, a high average selectivity and a very high stability. In addition, the silicate provides a gasoline with a very high octane ~umber and a very low olefins content.
Table F
Recirculation of the C4 product fraction results in a higher average selectivity and a higher stability whilst the very high average activity and very high product quality are maintained.
Table G
3o When a gasoline with a higher butenes content is used as the feed, then, at a comparable increase in arcmatics content, a much smaller loss of C5 is attained, in other words a higher selectivity of the quality improvement. Meanwhile the very high product quality is maintained.
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for improving the quality of a gasoline obtained by catalytic cracking, characterized in that the gasoline is con-tacted with a crystalline metal silicate which, after one hour's calcination in air at 500°C, has the following properties:
a) thermally stable up to a temperature of at least 600°C, b) an X-ray powder diffraction pattern in which the strong-est lines are the four lines mentioned in Table A.
c) in the formula which represents the composition of the silicate expressed in moles of the oxides and which, in addition to SiO2, includes both Fe2O3 and Al2O3, the SiO2/Fe2O3 molar ratio is 25-90 and the SiO2/Al2O3 molar ratio is 250-1200.
a) thermally stable up to a temperature of at least 600°C, b) an X-ray powder diffraction pattern in which the strong-est lines are the four lines mentioned in Table A.
c) in the formula which represents the composition of the silicate expressed in moles of the oxides and which, in addition to SiO2, includes both Fe2O3 and Al2O3, the SiO2/Fe2O3 molar ratio is 25-90 and the SiO2/Al2O3 molar ratio is 250-1200.
2. A process as claimed in claim 1, characterized in that the crystalline metal silicate has an alkali metal content of less than 0.05 %w.
3. A process as claimed in claim 1, 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-l.h-1.
4. A process as claimed in claim 1, characterized in that at least part of the C4? product fraction is recirculated.
5. A process as claimed in claim 1, characterized in that it is applied to a gasoline obtained by catalytic cracking which has an increased C3 and/or C4? olefins content.
6. A process as claimed in claim 5, characterized in that the increase of the olefins content of the gasoline has come about by carrying out the separation between the C4? fraction and the gasoline fraction of the cracked product in such a manner that at least part of the olefins which as a rule are withdrawn together with the C4? fraction, go into the gasoline fraction.
7. A process as claimed in claim 5, characterized in that the increase of the olefins content of the gasoline has come about by adding C3 and/or C4? olefins from an external source.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8202607 | 1982-06-28 | ||
| NL8202607 | 1982-06-28 | ||
| NL8204634 | 1982-11-30 | ||
| NL8204634A NL8204634A (en) | 1982-11-30 | 1982-11-30 | Improving quality of petroleum obtd. by catalytic cracking - by treatment with metal silicate catalyst contg. iron and aluminium, to give increased aromatic and lower olefin content |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1203496A true CA1203496A (en) | 1986-04-22 |
Family
ID=26645784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000427430A Expired CA1203496A (en) | 1982-06-28 | 1983-05-04 | Process for improving the quality of gasoline |
Country Status (7)
| Country | Link |
|---|---|
| AU (1) | AU554301B2 (en) |
| CA (1) | CA1203496A (en) |
| ES (1) | ES8403960A1 (en) |
| FR (1) | FR2537152B1 (en) |
| GB (1) | GB2122637B (en) |
| IT (1) | IT1170157B (en) |
| NZ (1) | NZ204691A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8616161D0 (en) * | 1986-07-02 | 1986-08-06 | Shell Int Research | Catalyst composition |
| DE68904417D1 (en) * | 1989-02-17 | 1993-02-25 | Council Scient Ind Res | REFORMING PROCESS FOR THE CATALYTIC CONVERSION OF HYDROCARBON FRACTIONS TO AROMATIC-rich HYDROCARBON MIXTURE. |
| JP3839565B2 (en) * | 1997-01-20 | 2006-11-01 | 日本碍子株式会社 | Synthesis method of high silica silicate molecular sieve |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8102470A (en) * | 1981-05-20 | 1982-12-16 | Shell Int Research | PROCESS FOR PREPARING AN AROMATIC HYDROCARBON MIXTURE |
-
1983
- 1983-05-04 CA CA000427430A patent/CA1203496A/en not_active Expired
- 1983-06-24 IT IT21787/83A patent/IT1170157B/en active
- 1983-06-24 GB GB08317250A patent/GB2122637B/en not_active Expired
- 1983-06-24 AU AU16209/83A patent/AU554301B2/en not_active Ceased
- 1983-06-24 NZ NZ204691A patent/NZ204691A/en unknown
- 1983-06-24 FR FR8310484A patent/FR2537152B1/en not_active Expired
- 1983-06-25 ES ES523592A patent/ES8403960A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2537152A1 (en) | 1984-06-08 |
| GB8317250D0 (en) | 1983-07-27 |
| GB2122637B (en) | 1986-05-29 |
| ES523592A0 (en) | 1984-04-01 |
| IT8321787A0 (en) | 1983-06-24 |
| GB2122637A (en) | 1984-01-18 |
| AU1620983A (en) | 1984-01-05 |
| FR2537152B1 (en) | 1988-04-01 |
| NZ204691A (en) | 1985-03-20 |
| ES8403960A1 (en) | 1984-04-01 |
| IT1170157B (en) | 1987-06-03 |
| AU554301B2 (en) | 1986-08-14 |
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