GB2031014A - Creación de Inventos y Patentes con Inteligencia Artificial

GB2031014A – Producing gasoline form c3/c4 olefins
– Google Patents

GB2031014A – Producing gasoline form c3/c4 olefins
– Google Patents
Producing gasoline form c3/c4 olefins

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Publication number
GB2031014A

GB2031014A
GB7930029A
GB7930029A
GB2031014A
GB 2031014 A
GB2031014 A
GB 2031014A
GB 7930029 A
GB7930029 A
GB 7930029A
GB 7930029 A
GB7930029 A
GB 7930029A
GB 2031014 A
GB2031014 A
GB 2031014A
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United Kingdom
Prior art keywords
process according
isobutane
cut
gasoline
methanol
Prior art date
1978-08-31
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.)

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GB7930029A
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GB2031014B
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IFP Energies Nouvelles IFPEN

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IFP Energies Nouvelles IFPEN
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1978-08-31
Filing date
1979-08-30
Publication date
1980-04-16

1979-08-30
Application filed by IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN

1980-04-16
Publication of GB2031014A
publication
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patent/GB2031014A/en

1982-08-25
Application granted
granted
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1982-08-25
Publication of GB2031014B
publication
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patent/GB2031014B/en

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Classifications

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms

C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons

C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation

C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond

C07C2/08—Catalytic processes

C07C2/26—Catalytic processes with hydrides or organic compounds

C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides

C—CHEMISTRY; METALLURGY

C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT

C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS

C10L1/00—Liquid carbonaceous fuels

C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only

C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds

C07C2527/06—Halogens; Compounds thereof

C07C2527/08—Halides

C07C2527/12—Fluorides

C07C2527/1206—Hydrogen fluoride

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds

C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides

C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides

C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE

Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

Y02P30/00—Technologies relating to oil refining and petrochemical industry

Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Description

1 GB 2 031 014 A 1
SPECIFICATION Process for producing gasoline of high octane number. in particular load-free gasoline
This invention concerns a process for producing gasoline or a gasoline component of high octane number which may be used without addition of antiknock agent such as tetraethyl lead.
THE PROBLEM Up to now lead-free gasoline was mainly produced by:
– Very severe catalytic reforming of naphtha, or – Alkylation with isobutane of C,-C4 catalytic cracking cuts containing olefins.
Lead-free gasoline, produced by catalytic reforming of high severity, is not ideal with respect to pollution and public health. As a matter of fact it contains benzene, whose vapor has proved very toxic. 10 On the contrary, alkylation yields gasoline which is satisfactory as concerns both the ecological point of view and the purely technical engine problems.
Unhappily this route is essentially restrained by the isobutane shortage.
More than ever it is necessary to find a process to obtain valuable products from olefinic C,_C4 cuts, which process is self-sufficient in isobutane and capable to produce gasoline of equivalent quality. 15 The reaction between isobutane and a C. or C4 olefin being equimolecular, it has been calculated that the required theoretical amount of isobutane is 1.38 kg for 1 kg of propylene and 1.035 kg for 1 kg of butenes.
It has been observed that the C,_C4 catalytic cracking cuts suffer generally from the drawback of a heavy lack of balance with respect to the isobutane content which is far from being sufficient to satisfy 20 the above stoichiometry. A typical cut has the following composition (% by weight):
propene propane : 25.00 : 8.35 isobutane: 23.35 isobutene: 10.65 25 n. 1-butene: 6.65 n.2-butene: 18.00.
n C4 (n-butane): 8.00 The above composition shows that the isobutane proportion is hardly one third of the 30 stoichiometrical proportion of olefins.
STATE OF THE ART The lack of balance of C3_C4 cuts is well known. For example U.S. patent specification
3,758,628 proposes to obviate it by using simultaneously a hydrocracking unit and a catalytic cracking unit. But, as shown above, the present trend is towards a stagnation or even a reduction in the number and the capacity of the existing hydrocracking units. Moreover, hydrocracking is an expensive operation which 35 produces numerous products other than isobutane, which are not always valuable.
During the last years, attempts have been made to mix alcohols, ethers, etc…, with gasoline, either to improve the octane number or to meet with oil shortage of for other purposes.
Such attempts have been described for example, in U.S. patent specification No. 3,726,942 and
French patent 2,063,939.
It does not seem, however, that a really economical way of operation has been attained either as a result of a too high production cost or of insufficient gasoline performances.
THE INVENTION The-present invehtion resolves the above problem in a very new, simple and economical manner; it has for object, instead of finding an additional external source of isobutane, to modify the coMposition 45 of the C3-C4 Cut SO that said composition be closer to the stoichiometry of the alkylation reaction of olefins with isobutane.
It has also for object to improve the quality of the alkylate by modifying the composition of butenes in such a manner that the resulting products have a better octane number. This is achieved by providing for the alkylation of C4 olefins enriched with n-butenes and impoverished or made free of 50 propylene and isobutene. As a matter of fact, the alkylates obtained by reaction of isobutane with 2 GB 2 031 014 A 2 propylene or isobutene have an octane number which is not so high as those obtained by reacting isobutane with 2-butene; Research Octane Number: 92.7 when starting from isobutene, 96.8 and 96.2 respectively when starting from 1 -butene and 2-butene and about 90 when starting from propylene.
It must be noted that these values correspond to a conventional alkylation with sulfuric acid.
In the case of an alkylation with hydrofluoric acid W), higher values can be obtained, Le.:
91 for propylene, 95.9 for isobutene, 94.4 for 1 -butene, 97.6 for cis 2butene, 97.8 for trans 2butene.
Another object of the invention is to obtain gasoline or a gasoline component of high octane number, which can be used without lead additive.
According to the invention, the CC4 hydrocarbon charge, when not available as separate C3 and 10 C4 fractions, is fractionated to a first fraction (A) of high C, hydrocarbon content, particularly of high propylene content, and a second fraction (B) of high C4 hydrocarbon content, particularly of high isobutane, isobutene, 1 -butene and 2-butenes content.
The first fraction (A) is selectively oligomerized essentially to C, and C, olefinic hydrocarbons, with a major portion of C, olefinic hydrocarbons, to form a first fraction (1) of gasoline of high octane number (oligomerizate). The second fraction (B) is reacted with methanol, in the presence of an acid catalyst, so as to obtain methyl-tert.-butyl ether by reaction of isobutene with methanol. The product of this reaction is fractionated so as to separate the unreacted hydrocarbons from the methyl tert.-butyl ether which constitutes the second fraction (11) of high octane number gasoline.
The unreacted hydrocarbons are those from fraction (B) with however a zero content or, at least, a 20 decreased content of isobutene, due to the fact that the normal olefins practically did not react with methanol. In this hydrocarbon mixture, as a result of the lowering of the isobutene content, the isobutane/olefin ratio was increased and at least brought closer to the theoretical molar ratio of 1, if not reaching said value. This mixture is then subjected to aliphatic alkylation either as such or after addition of isobutane, said addition being however much smaller than that which would have been made when 25 omitting the step of etherification of isobutene. There is thus obtained an alkylate which constitutes the third fraction (111) of gasoline of high octane number.
The fractions 1, 11 and 111 can then be mixed, partly or completely, in order to obtain a gasoline or a gasoline component of high octane number which can be used without lead, either as such or in admixture with, for example, a reformate or other fractions in the gasoline range.
It is possible, if so desired, to proceed to a stabilization of fractions 1, 11 and Ill, either separately on each fraction or on their mixture.
DETAILED DESCRIPTION OF THE INVENTION
The hydrocarbon charge is preferably a C3_C4 catalytic cracking fraction. It may be available as a 35 C3_C4 mixture and must then be fractionated to a C3 fraction and a C4 fraction as above-mentioned; it may also be available as separate C3 and C4 fractions, for example as obtained by distillation of the effluents from a catalytic cracking unit.
The catalytic cracking may be of any type, for example a fluid catalytic cracking fed with a distillate of high saturated hydrocarbon content produced, for example, by direct distillation of crude oils. The 40 catalytic cracking processes are well known and a detailed description thereof is then unnecessary. The catalysts are, for example, silica-alumina, a clay or a zeolite. A detailed description is given, for example, in U.S. patent specification 3,758,628.
The C1_C4 fraction usually contains from 0.15 to 0.6 mole of isobutane per mole of olefins. With this condition, a typical composition by weight is as follows:
isobutane: 15 to 30% 45 propene: 15to35%.
isobutene: 5 to 15% 1-butene : 3to10% 2-butenes: 10to25% propane +n-butane: 8to30% 50 When the product obtained by catalytic cracking is already in the form of separate C, and C4 cuts, their composition is for example as follows (by weight):
C3 cut: propane propylene : 15-50% : 50-85% 3 GB 2 031 014 A 3 C4CUt: n-butane isobutane isobutene 1-butene 5-20% 20-50% 10-25% 5-15% 2-butene: 10-40% 5 The fractionation between C3 and C4 fractions is easy to achieve by distillation. It is not necessary that the C3 fraction be entirely free from C4 hydrocarbons and reversely.
The oligornerization of the C3 hydrocarbon cut is preferably performed in the liquid phase by contacting said cut with a catalyst obtained by contacting (or reacting) a compound of a transition metal 10 0 from groups IV to Vill with an alkylaluminum, preferably a compound of nickel with a hydrocarbylaluminum halide, for example a monohydrocarbylaluminum dihalide or a hydrocarbylaluminum sesquichloride. The reaction is conducted in most cases at a temperature from 0 to 601C, preferably from 30 to 501C. The nickel compound may, for example, consist of a carboxylate, an acetylacetonate, a phosphine complex of a nickel salt such as a chloride or an acetylacetonate. The reaction is well known and it can be referred, for example, to the following patent specifications: U.S.P.
2,969,408 and 3,655,810 and French patent 1,591,577. As state of the art, there will be mentioned U.S. patents 3,032,544; 3,390,201; 3,485,881; 3,321,546; 3,482,001 and 3, 467,726.
Compounds of other metals than nickel may also be used, such as, for example, compounds of titanium (U.S.P. 3,686,350), cobalt (U.S.P. 3,686,353), chromium (U.S.P. 3,709,954 and 3,726,939),20 0 vanadium (U.S.P. 3,737,476), tungsten (U.S.P. 3,784,629), etc Preference is given to the combination of a nickel compound with a dichloroalkylaluminum, in view of its better selectivity to produce olefins with 6 carbon atoms.
When the oligomerization has been completed, there is obtained an oligomerizate (1) which constitutes one of the desired gasoline fractions.
Other oligomerization techniques may be used, such, for example, as the treatment with a catalyst of silica-alumina, phosphoric acid, boron trifluorlde, aluminum trichloride, etc…
The results are however less satisfactory with respect to the composition of the oligornerizate which contains more heavier oligomers having 9, 12 and 15 carbon atoms; moreover the catalyst is difficult to handle, it must be changed frequently and it must be operated under relatively high pressure. 30 The state of the art is given, for example, by U.S. patent specifications 3,769,363; 3,833,678; 3,758,627 and 3,887,634.
The reaction between the isobutene of the C4 cut and methanol is performed in the presence of an acid catalyst, for example sulfuric acid, hydrofluoric acid, aluminum chloride and boron fluoride. However, it is preferred to make use of carbonaceous materials containing _S03H groups, for example 35 !5 sulfonated carbons (e.g. X orAX Nalcite, H ZeO-Karb), sulfonated phenol-formaldehyde resins (for example Amberlite IR-1 or IR-1 00, Nalcite MX), sulfonated cournarone- indene polymers or, preferably, sulfonated polystyrene-divinylbenzene resins, for example Dowex 50, Nalcite HCR and Amberlyst 15.
When proceeding in a continuous manner, the volume of charge treated per volume of catalyst 40 0 and per hour is usually from 0.5 to 20. Usual operating conditions are a temperature from 20 to 1500C, preferably from 40 to 1 001C, a proportion of 1 to 10 moles of methanol per mole of isobutene, an alcohol excess favouring the reaction.
The etherification reaction is well known and described for example in U. S. patent specifications
2,480,940; 3,037,052 and 3,281,475.
The alkylation reaction is conducted under conventional conditions for aliphatic alkylation. The known catalysts for the reaction of isobutane with butenes may be used, hydrofluoric acid being preferred. Othelr catalysts are sulfuric acid, phosphoric acid or Friedel and Crafts catalysts.
As state of the art, there will be mentioned U.S. patent specifications 2, 308,560; 2,320,199;
2,429,205; 2,768,987; 2,818,458;2,914,592; 2,920,124;2,429,205 and 3,855, 344, among others.50 0 The invention is by no way limited to particular conditions of the well known alkylation reaction.
There is thus obtained an alkylate (111) which constitutes the third gasoline fraction of high octane number and can be admixed with the oligornerizate (1) and the ether (11). Preferably at least 90% by weight of the final gasoline distils between 40 and 2201C.
The invention is illustrated by the accompanying drawing.
A catalytic cracking effluent (line 1) or preferably a CS_C4 fraction from said effluent is fractionated in a distillation unit diagrammatically shown as a column 2, into a C, and a C4 fractions. The C3 fraction is fed, through line 3, to the oligornerization unit 4. The effluent from said unit is supplied, through duct 5, to column 6 to be fractionated. The light hydrocarbons are separated through line 7; they may be recycled to unit 4. There is recovered an oligornerization gasoline fraction through line 8. Its 60 0 distillation range is between about 40 and 2200C, but it mainly contains propylene dimers. This fraction 4 GB 2 031 014 A 4 is fed to the gasoline «pool».
The C4 fraction, withdrawn from line 9, is supplied to the alkylation unit 10, fed with methanol through line 11. This methanol is pa rtly supplied from the recycle duct 12. At the outlet of the alkylation unit, the product is conveyed through line 13 to the stabilization column 14. At the top (line 15) there are recovered unreacted C4 hydrocarbons together with unconverted methanol; at the bottom there is recovered methyl tert. butyl ether (line 16).
The C4 cut may be subjected to water washing in order to remove therefrom at least one part of the unconverted methanol; the water is introduced through line 17 into the washer 18. By decantation, there is recovered an aqueous phase and a C4 hydrocarbon phase. The aqueous phase is fed, through line 19, to the distillation column 20: methanol is recycled through line 12 and water may be fed back 10 to the washing unit through line 17. The C4 hydrocarbon phase is dried, if required, and fed through line 21 to the alkylation unit 22. Additional isobutane may be introduced, when necessary, through line 23.
The alkylate is fed, through line 25, to the stabilization column 26. At the top thereof, there is essentially withdrawn n-butane and at the bottom the desired alkylate. The latter, discharged through line 27, may join the other gasoline fractions (lines 8 and 16) to provide a gasoline usable without lead (line 28). 15 EXAMPLE The composition of the C,/C, hydrocarbon charge and of the obtained fractions is given in the following Table. The operation has been conducted according to the diagram of the accompanying drawing. 20 The operating conditions were as follows: First, the C3 and C 4 hydrocarbons have been separated by distillation. The propylene oligomerization unit was operated with a catalyst formed of nickel octoate and dichloroethylaluminum in an atomic ratio A]/Ni of 15:1 at a concentration of 20 parts by weight of nickel, per million of parts, at a temperature of 40-451C, under a pressure sufficient to maintain propylene and propane in the liquid phase (about 10 bars) and with a total residence time of 3 hours. At 25 the outlet of the reactor, the catalyst has been first neutralized with anhydrous ammonia and then washed with water to remove the catalyst residues. The effluent has then been fed to a stabilization column: at the top unreacted propane and propylene were recovered and at the bottom the stabilized oligomerizate.
The C4 hydrocarbon fraction has been fed with methanol to an etherification reactor operating 30 according to the following conditions:
15) Catalyst: ion exchange resin based on polystyrene cross-linked with divinyibenzend (Amberlyst Operating conditions: 35 temperature 50-900C pressure 10-20 bars molar ratio methanol/isobutene: 1.02 The product is distilled and there is recovered at the top an azeotrope of residual C4 hydrocarbon/methanol and at the bottom the methyl tertiobutyl ether (MTBE).
The residual C4 cut is washed with water to recover unconverted methanol and then dried. 40 The washing aqueous phase is distilled to recover methanol which is recycled to the etherification reactor.
recycled.
The residual C4 cut, after washing and drying, is fed to the alkylation reactor, operated as follows:
Catalyst: hydrofluoric acid at 85.9% by weight. Temperature: 27-38OC; pressure: 14 bars; molar ratio isobutane/olefins: 6/1 Couhter-current reactor with recycling of unconverted isobutane. After decaQtation, the organic phase is fractionated to give the alkylate and the isobutane to be The alkylate has been fed to a stabilization column, in order to separate n-butane from the traces of residual isobutane. An alkylate is recovered which is admixed with the methyl tert.-butyl ether (MTBE) 50 and the oligomerizate. The resultant mixture consists of a gasoline having a research octane number (RON) without lead of 101.
It is thus made apparent that a synergic effect occurs between the components since the theoretical RON, calculated from the following values:
Oligomerizate RON: 95.5 55 Alkylate RON: 94.5 MTBE : 115 GB 2 031 014 A 5 is only 98.2.
The carburant mixture obtained according to the invention has a volumic mass at 200C of 0.710 which is typical of a light gasoline; with respect to distillation, its initial point is 401C, 10% are distilled at 550C, 50% at 8WC, 90% at 11 30C and its final distillation point is 1880C.
The present process may be used with CC4 olefinic fractions having another origin than catalytic 5 cracking, for example with coking CA Cuts.
0) COMPOSITION (WEIGHT PER TIME UNIT) Stabili zed Stabi 1 i – Initial oligomer- Fresh Recycled Isobutane zed charge C3 cut C4 Out i zate methanol methanol MTIBE Water cut alkylate (line 1) (line 3) (line 9) (line 8) 1 (line 11) (line 12) (line 16) (line 17) (line 23) (1 ine 27) Propylene 15.0 15.0 Propane 5.0 5.0 Isobutane 14.0 14.0 2.1 Isobutane 6.4 6.4 1-butene 4.0 4.0 2-butenes 10.8 10.8 n-butane 4.8 4.8 2.9 Oligomerizate 14.8 Methanol 3.5 0.3 MTIBE 9.6 Alkylate 30.9 Total gasoline (40-188 & C) Water 4 Final gasoline (line 28) 55.3 1 11 a) W rli 0 W 0 4h CD 7 GB 2 031 014 A

Claims (11)

1. A process for producing gasoline of high octane number from C3 and C, olefinic cuts or mixtures thereof, comprising the following steps:
a) – oligomerizing propylene of the C, cut, so asto obtain an oligomerizate (1) distilling within the gasoline range, b) – reacting the C4 cut with methanol in the presence of an acid catalyst, under etherification conditions, so as to obtain methyl tertiobutyl ether by reaction between isobutene and methanol, C) – fractionating the product from step (b) to obtain separately methyl tert.-butyl ether, forming a second gasoline fraction (11) of high octane number, and unreacted C4 hydrocarbons, d) – alkylating the unreacted C4 hydrocarbons obtained instep (c) by reaction of isobutane with the 10 C4 olefins, in the presence of an alkylation catalyst, in the conditions of the aliphatic alkylation reaction, to obtain an alkylate which forms the third gasoline fraction (111) of high octane number, and e) – admixing at least one portion of the alkylate (111) with at least one portion of the fraction (11) and at least one portion of the oligomerizate (1), to obtain the desired gasoline of high octane number. 15

2. A process according to claim 1 wherein the C3 and C4 cuts used as starting material are obtained from a previous fractional distillation of a CA catalytic cracking cut.

3. A process according to claim 1 or 2 wherein oligomerization is conducted in the presence of a catalyst obtained by contacting a compound of a metal from groups IV to VI 11 with an alkylaluminum compound.

4. A process according to claim 3, wherein the alkylaluminum compound is a hydrocarbylaluminum halide and the metal compound is a nickel compound.

5. A process according to one of claims 1 to 4, wherein the reaction between the C4 cut and methanol is conducted in the presence of a sulfonic resin.

6. A process according to one of claims 1 to 5, wherein the alkylation of the C4 hydrocarbons is 25 performed in the presence of hydrofluoric acid.

7. A process according to one of claims 1 to 6, wherein, when the isobutane/C4 olefins ratio is lower than 1, isobutane is added to increase this ratio to at least 1.

8. A process according to claim 2, wherein the common CC4 starting cut has the following composition, by weight:
propylene isobutane isobutene 1-butene 2-butenes propane + n-butane : 15-35% : 15-30% 5-15% 3-10% : 10-25% 8-30%

9. A process according to one of claims 1 to 7, wherein the C3 and the C 4 cuts have the following respective compositions, by weight:
C3 CUt C4 CUt propane: 15-50% n-butane: 5-20% 40 propylene: 50-85% isobutane: 20-50Yo isobutene: 10-25% 1-butene: 5-15% 2-butene: 10-40% 8 GB 2 031 014 A 8

10. A process according to Claim 1, carried out in apparatus substantially as hereinbefore described with reference to the drawing.

11. A process according to Claim 1, carried out substantially as hereinbefore described in the Example.
Printed for Her Majesty’s Stationery Office by the Courier Press, Leamington Spa, 1980. Published by the Patent Offici, 25 Southampton Buildings, London, WC2A 1 AY, from which copies may be obtained.
4 k :1

GB7930029A
1978-08-31
1979-08-30
Producing gasoline form c3/c4 olefins

Expired

GB2031014B
(en)

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FR7825359A

FR2434861A1
(en)

1978-08-31
1978-08-31

PROCESS FOR PRODUCING HIGH-INDEX OCTANE GASOLINE AND IN PARTICULAR LEAD-FREE GASOLINE

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1982-08-25

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Producing gasoline form c3/c4 olefins

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active
Granted

1979

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DE
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patent/DE2934612A1/en
not_active
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1979-08-30
CA
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patent/CA1129366A/en
not_active
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1979-08-30
MX
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patent/MX6840E/en
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GB
GB7930029A
patent/GB2031014B/en
not_active
Expired

1979-08-31
US
US06/071,503
patent/US4270929A/en
not_active
Expired – Lifetime

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JP
JP11234479A
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1984-08-22
Phillips Petroleum Co
Processes for the production and recovery of methyl tertiary butyl ether

Also Published As

Publication number
Publication date

MX6840E
(en)

1986-08-20

FR2434861A1
(en)

1980-03-28

US4270929A
(en)

1981-06-02

JPS5536292A
(en)

1980-03-13

GB2031014B
(en)

1982-08-25

FR2434861B1
(en)

1982-03-19

CA1129366A
(en)

1982-08-10

DE2934612A1
(en)

1980-03-06

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