CN100575460C - The method of aliphatic series gasoline component and the described gasoline component of preparation - Google Patents
The method of aliphatic series gasoline component and the described gasoline component of preparation Download PDFInfo
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- CN100575460C CN100575460C CN200580013675A CN200580013675A CN100575460C CN 100575460 C CN100575460 C CN 100575460C CN 200580013675 A CN200580013675 A CN 200580013675A CN 200580013675 A CN200580013675 A CN 200580013675A CN 100575460 C CN100575460 C CN 100575460C
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Abstract
The aliphatic series gasoline component, it comprises greater than the compound of the trimethylammonium replacement of 90wt% and the mixture of the compound that monomethyl replaces, wherein the weight ratio of trimethylammonium compound and monomethylation compound is at least 0.03, and wherein said compound can be paraffinic hydrocarbons and alkene.The invention still further relates to the method for preparing aliphatic gasoline component as follows: (a) in riser reactor, under 450-650 ℃ temperature, between 1-10 under the duration of contact of second, with at the ratio of catalyzer and oil under 2-20kg/kg, fischer-tropsch synthesis product is contacted with the catalyst system that contains catalyzer, and wherein said catalyzer contains acidic matrix and large pore molecular sieve; (b) from the product of step (a), separate gasoline fraction and the cut that contains Trimethylmethane and iso-butylene; (c) make the Trimethylmethane and the iso-butylene that obtain in the step (b) carry out alkylation step, with the pentane of preparation trimethylammonium replacement; The product of the pentane that is rich in the trimethylammonium replacement that (d) obtains in gasoline fraction that obtains in the combination step (b) and the step (c).
Description
Technical field
The present invention relates to aliphatic gasoline component, gasoline prescription and prepare the method for described gasoline component.
Background technology
Known can be by Fisher-Tropsch derived sintetics preparation ebullient paraffin products in gasoline-range.But the gasoline that is had acceptable octane value by the fischer-tropsch products preparation is also remarkable.This is to be made up of the normal paraffin with the contribution of low octane rating or low octane rating because this fischer-tropsch products itself is most of.Having carried out various trials provides and can have the method for the gasoline of acceptable octane value by the fischer-tropsch products preparation.
EP-A-512635 discloses a kind of method, wherein is 85 gasoline by fischer-tropsch process acquisition motor-method octane number by hydroisomerisation process.This method also comprises uses zeolite beds separation of normal paraffins and isoparaffin.
US-A-6436278 discloses the method similar with EP-A-512635.Embodiment has been described the gasoline that directly obtains in hydroisomerisation step octane value is 43.After the gasoline fraction in the enrichment isoparaffin, obtain 68 octane value.
US-A-20020111521 discloses the method for preparing gasoline, wherein by fischer-tropsch wax being placed so-called typical case (Paragon) reactor to obtain light alkene.These light alkenes are oligomeric subsequently, to obtain size range between C
12-C
20Highly branched isoolefine.
EP-A-454256 discloses the method that is prepared light alkene by fischer-tropsch products, wherein by in moving-burden bed reactor, under 580-700 ℃ temperature,, described fischer-tropsch products is contacted with the catalyzer that contains ZSM-5 under the ratio of the catalyzer of 65-86kg/kg and oil.
US-A-4684756 discloses the fischer-tropsch wax that obtains by catalytic cracking and has directly prepared the method for gasoline fraction in the catalytic fischer-tropsch process of iron.The productive rate of gasoline is 57.2wt%.
The shortcoming that comprises the part aforesaid method of hydrotreatment is that isomerized product mainly is the monomethyl paraffinic hydrocarbons.Even after the enrichment isoparaffin, octane value is still lower.
The purpose of this invention is to provide paraffinic hydrocarbons gasoline component with acceptable motor-method octane number and the method for preparing this gasoline by the fischer-tropsch products high productivity.
Summary of the invention
The present invention relates to following gasoline component: the aliphatic gasoline component that contains the mixture of the compound that the compound that replaces greater than the trimethylammonium of 90wt% and monomethyl replace, wherein the weight ratio of trimethylammonium compound and monomethylation compound is at least 0.03, and wherein said compound can be paraffinic hydrocarbons and alkene.
The invention still further relates to the Fuel Petroleum composition, it comprise above-mentioned aliphatic gasoline component, one or more additives, between the aromaticity content (measuring) of 1-22vol%, motor-method octane number by ASTM D5580-95 greater than 90 and sulphur content be lower than 15ppmw (measuring) by ASTM D5453-93.
The invention still further relates to the method for preparing aliphatic gasoline component as follows:
(a) in riser reactor, under 450-650 ℃ temperature, between 1-10 under the duration of contact of second, with at the ratio of catalyzer and oil under 2-20kg/kg, fischer-tropsch synthesis product is contacted with the catalyst system that contains catalyzer, and wherein said catalyzer contains acidic matrix and large pore molecular sieve;
(b) from the product of step (a), separate gasoline fraction and the cut that contains Trimethylmethane and iso-butylene;
(c) make the Trimethylmethane and the iso-butylene that obtain in the step (b) carry out alkylation step, with the pentane of preparation trimethylammonium replacement; With
The product of the pentane that is rich in the trimethylammonium replacement that (d) obtains in gasoline fraction that obtains in the combination step (b) and the step (c).
Embodiment
The applicant finds, can obtain aliphatic gasoline by catalytic cracking fischer-tropsch synthesis product and combination alkylated reaction subsequently.In preferred embodiments, the fischer-tropsch products of phase counterweight is as the raw material of catalytic cracking step (a).The gasoline fraction with many branched paraffin or alkene that obtains in the enriching step (c) is to increase octane value to making gasoline be suitable as the degree of Fuel Petroleum or blended into gasoline thing component.Further advantage be except optional hydrofined gasoline blend to satisfy the high olefin specification that some field requires, do not need hydrotreatment.For example, can directly use fischer-tropsch synthesis product in the method for the invention under needn't the situation of hydrotreated feed.Another advantage is to utilize the processes well known of the technology that becomes known for fluid catalytic cracking (FCC) step (a) and alkylation step (c).
Fischer-tropsch synthesis product can be any reaction product that obtains when carrying out known F-T synthesis reaction in principle.Preferably in step (a), use the fischer-tropsch products of phase counterweight.This heavy feed stock preferably has the compound that 30wt% at least has at least 30 carbon atoms, preferably 50wt% and more preferably 55wt% at least at least.In addition, in the fischer-tropsch products, have at least 60 or the compound of more a plurality of carbon atoms be at least 0.2 with weight ratio, preferably at least 0.4 and more preferably at least 0.55 with compound of at least 30 carbon atoms.Preferably, fischer-tropsch products comprises that ASF-α value (the Anderson-Schulz-Flory chainpropagation factor) is at least 0.925 C
20+ cut, preferably at least 0.935, more preferably at least 0.945, even more preferably at least 0.955.
The initial boiling point scope of the fischer-tropsch products that uses in step (a) can be suitably for being lower than 200 ℃ until 450 ℃.Preferably, in step (a), use before the fischer-tropsch synthesis product, from described fischer-tropsch synthesis product, isolate and have any compound and any compound of boiling point in this scope that is less than or equal to 4 carbon atoms.The applicant finds, begins (therefore being included in ebullient fischer-tropsch distillate in the gasoline-range) by this fischer-tropsch products, can realize high gasoline yield.Therefore, with respect to fischer-tropsch products, can realize high gasoline yield.
Any method of fischer-tropsch products that can be by obtaining the phase counterweight obtains the fischer-tropsch synthesis product of phase counterweight.Be not that all fischer-tropsch process all obtain this heavy product.Preferable methods is the catalytic fischer-tropsch process of cobalt.The example of suitable fischer-tropsch process is disclosed in WO-A-9934917 and AU-A-698391.These technologies can obtain above-described fischer-tropsch products.
The preferred catalyst of fischer-tropsch products that is used to obtain the phase counterweight is suitably for containing the catalyzer of cobalt, the described catalyzer that contains cobalt can obtain as follows: (aa) mix (1) titanium oxide or precursors of titanium oxide, (2) liquid and (3) cobalt compound to form mixture, wherein said cobalt compound is insoluble to small part in described liquid consumption; (bb) moulding and the dry mixture that so obtains; (cc) the calcining composition that obtains like this.
Preferably, the cobalt compound of 50wt% is insoluble in described liquid consumption at least, more preferably 70wt% and even more preferably 80wt% and most preferably 90wt% at least at least at least.Preferably, cobalt compound is cobalt metal powder, cobalt hydroxide or cobalt/cobalt oxide, more preferably Co (OH)
2Or Co
3O
4Preferably, the consumption of cobalt compound is maximum 60wt% of refractory oxide consumption, more preferably between 10-40wt%.Preferably, catalyzer contains at least a promoter metals, preferred manganese, vanadium, rhenium, ruthenium, zirconium, titanium or chromium, most preferably manganese.The consumption of promoter metals preferably makes the atomic ratio of cobalt and promoter metals be at least 4, and more preferably at least 5.Suitably, at least a promoter metals compound is present in the step (aa).Suitably, by precipitation, optional then calcining obtains cobalt compound.Preferably, by co-precipitation,, obtain the compound of cobalt compound and at least a promoter metals more preferably by the co-precipitation under constant pH.Preferably, in the presence of partial oxidation titanium or precursors of titanium oxide at least, preferably in the presence of all titanium oxide or precursors of titanium oxide, the precipitate cobalt compound.Preferably, carry out the mixing of step (aa) by kneading or grinding.Subsequently by granulation, extrude, granulation or pulverizing, preferably by extruding, make the mixture forming of acquisition like this.Preferably, the solids content scope of gained mixture is 30-90wt%, preferred 50-80wt%.Preferably, the mixture that forms in step (aa) is a slurry, and makes the slurry moulding and the drying of acquisition like this by spraying drying.Preferably, the solids content scope of gained slurry is 1-30wt%, more preferably 5-20wt%.Preferably, calcining under 400-750 ℃ temperature, described temperature is more preferably between 500-650 ℃.Further details is disclosed in WO-A-9934917.
Typically under scope is 125-350 ℃, preferred 175-275 ℃ temperature, carry out fischer-tropsch process.Pressure range typically is 5-150bara, preferred 5-80bara, particularly 5-70bara.Hydrogen (H
2) and carbon monoxide (synthetic gas) typically be that the mol ratio of 0.5-2.5 is fed in this technology with the scope.In the method for the invention, the gas hourly space velocity of synthetic gas (GHSV) can change in wide region, and scope typically is 400-10000N1/1/h, for example 400-4000N1/1/h.Term GHSV is well known in the art, and it relates to wherein under STP condition (0 ℃ and 1bara), does not promptly comprise the volume (N1 of unit, i.e. standard liter) of the synthetic gas that intergranular void volume contacts in 1 hour with 1 liter of granules of catalyst.Under the situation of stationary catalyst bed, GHSV also can be expressed as every liter of catalyst bed and promptly comprise intergranular void volume.Fischer-tropsch is synthetic can to carry out in fixed bed in slurry-phase reactor or preferably.Further details is disclosed in WO-A-9934917.
Can pass through known method, for example combination of partial oxidation and steam reformation and these technologies is begun by (hydrogen) carbon raw material, obtains synthetic gas.The example of possible raw material is the residual fraction of Sweet natural gas, associated gas, refinery flares and crude oil, coal, refinery coke and biomass such as timber.Partial oxidation can be by catalysis or not by catalysis.Steam reformation can be that for example conventional steam reformation, self-heating (ATR) reformed and convective steam reformer.The example of suitable partial oxidation technology is Shell gasifying process and Shell coal gasifying process.
Fischer-tropsch products does not contain or contains considerably less sulfur-bearing and nitrogen compound.This is typical for the product that is obtained by the Fischer-Tropsch reaction of using impure hardly synthetic gas.The content of sulphur and nitrogen is usually less than limit of detection, and this limit of detection is generally 5ppm and is 1ppm for nitrogen for sulphur.
Employed catalyst system comprises the catalyzer that contains matrix and macrovoid molecular sieve at least in the step (a).Suitable macrovoid examples of molecular sieve is faujusite (FAU) type, for example zeolite Y, overstable zeolite Y and X zeolite.Matrix optimization is an acidic matrix.Acidic matrix comprises amorphous alumina suitably, and the catalyzer that is preferably greater than 10wt% is an amorphous alumina.Matrix can further comprise for example aluminum phosphate, clay and silicon oxide and composition thereof.Amorphous alumina also can be used as tackiness agent, has the matrix of enough adhesive function with suitable bonding molecular sieve to provide.The example of appropriate catalyst is the commercially available catalyzer that uses in fluid catalytic cracking process, and described catalyzer contains zeolite Y as molecular sieve with comprise aluminum oxide in the substrate at least.
Raw material and catalyzer contact temperature between 450-650 ℃.More preferably this temperature is higher than 475 ℃ and even more preferably be higher than 500 ℃.Observe good gasoline yield being higher than under 600 ℃ the temperature.Yet the temperature that is higher than 600 ℃ will cause heat cracking reaction, and form undesirable gaseous product such as methane and ethane.Owing to this reason, temperature is more preferably less than 600 ℃.This technology can be carried out in various types of reactors.Because compare with the FCC technology of operating at petroleum derived feed, the generation of coke is less relatively, therefore may carry out this technology in fixed-bed reactor.For regenerated catalyst, still preferred streams fluidized bed reactor or riser reactor more simply.If carry out this technology in riser reactor, then preferred duration of contact is between 1-10 second with more preferably between 2-7 second.The ratio of catalyzer and oil is preferably between 2-20kg/kg.Have been found that be lower than 15 and even the ratio of the low catalyst that is lower than 10kg/kg and oil under can obtain good result.
This is favourable, because the higher output of the unit's of this means catalyzer causes for example littler equipment, catalyst inventory still less, energy requirement still less and/or higher output.
Catalyst system also can advantageously comprise the molecular sieve of intermediate pore size, thereby also obtains to be only second to the propylene of the high yield of gasoline fraction.The molecular sieve of preferred intermediate pore size is zeolite beta, erionite, ferrierite, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23 or ZSM-57.To be present in the whole molecular sieves in this technology, the crystalline weight fraction of medium hole is preferably between 2-20wt%.Mesoporous molecular sieve can make up or be present in different catalyst particles intragranulars with large pore molecular sieve in a granules of catalyst.Owing to putting into practice reason, macropore preferably is present in different catalyst particles intragranulars with mesoporous molecular sieve.For example, therefore the operator can add two kinds of catalyst components of catalyst system in this technology with different interpolation flows.Because two kinds of deactivation rate that catalyzer is different, this point may be requirement.The catalyzer that contains mesoporous molecular sieve also can comprise above-mentioned matrix at the large pore molecular sieve granules of catalyst.Suitable matrix is aluminum oxide.Can make the molecular sieve dealuminzation by for example steam or other known technology.
Have been found that, in riser reactor, under the ratio of preferred catalyzer and oil, the composition of macrovoid molecular sieve (the more preferably molecular sieve of FAU type) and the molecular sieve combination of intermediate pore size is important for the highly selective that realizes required light alkene (for example particularly propylene and iso-butylene).The applicant finds, carries out method of the present invention by adopting the large pore molecular sieve (the more preferably molecular sieve of FAU type) and the molecular sieve combination of intermediate pore size as mentioned above, not only improves the productive rate of light alkene, and increases the productive rate of Trimethylmethane and iso-butylene.When the similar technology of carrying out is compared, obtain the Trimethylmethane of twice content sometimes when with the catalyzer that do not add intermediate pore size.
In step (b), gasoline fraction is separated with the cut that is rich in iso-butylene and Trimethylmethane with the product of step (a).Carry out described fraction separation by distillation suitably.In the present invention, gasoline or gasoline fraction be greater than 90wt% between 25-215 ℃ of following ebullient cut, be preferably greater than 95wt% and in described boiling range, seethe with excitement.Can saturated suitably part iso-butylene, so that obtain to be used for the iso-butylene of alkylation step (c) and the stoichiometric reaction ratio of Trimethylmethane.
In step (c), make iso-butylene and Trimethylmethane carry out alkylated reaction, with the preparation pure isooctane.Except iso-butylene, other alkene such as the C that in step (a), obtain
3-C
8Alkene also can be the part of raw material for alkylation.Can use known method to carry out alkylation step, for example at " The Process:A new solid acid catalyst gasolinealkylation technology ", NPRA 2002 Annual Meeting, March 17-19, AlkyClean method described in 2002, the sulfuric acid alkylation method, for example as Lerner, H., " Exxon sulfuric acid alkylation technology ", Handbook ofPetroleum Refining Processes, the 2nd edition, R.A.Meyers edits, described in the pp.1.3-1.14
Fixed bed alkylation (FBA) technology and indirect alkylation of UOP (InAlk) and alkylene method.In US-A-4125566, can find other reference of alkylation.
In step (c), aliphatic cpd, particularly pure isooctane that the preparation trimethylammonium replaces.This compound has high octane value, and the gasoline fraction by these compounds of blend and acquisition in step (b) obtains aliphatic gasoline, and compares by the method for prior art is attainable in the past, and described aliphatic gasoline has improved octane value.
The invention still further relates to the following aliphatic gasoline that can obtain by aforesaid method: the aliphatic gasoline component that contains the mixture of the compound that compound that the trimethylammonium greater than 90wt% replaces and monomethyl replace, wherein the weight ratio of trimethylammonium compound and monomethylation compound is at least 0.03, and wherein said compound can be paraffinic hydrocarbons and alkene.The weight ratio of trimethylammonium compound and monomethylation compound is preferably greater than 0.05.Preferably, the content of the compound that this trimethylammonium of ebullient replaces in gasoline-range is high as far as possible, and this is because they have the inherent high-octane rating.In the method for the invention, this ratio is not higher than 0.4 usually, is not higher than 0.3 suitably.Preferably, the content of pure isooctane is 2-20wt%.Can measure the compound of trimethylammonium replacement and the content of the compound that monomethyl replaces by the vapor-phase chromatography described in the ASTM D-6730.
Randomly, make aliphatic gasoline hydrogenation, so that reduce olefin(e) centent, to satisfy effective Fuel Petroleum specification for some markets.
The invention still further relates to above gasoline fraction as the purposes that is applicable to the Fuel Petroleum composition part of spark ignition engine.More preferably, this fuel composition comprise above-described aliphatic gasoline component, one or more fuel dopes, between the aromaticity content (measuring) of 1-22vol%, motor-method octane number by ASTM D5580-95 greater than 90 and sulphur content be lower than 15ppmw (measuring) by ASTM D5453-93.Said composition also can comprise by mineral crude oil and/or the Fuel Petroleum that obtained by pyrolytic process, and its primary product is a light alkene.Described additive typically is and well known to a person skilled in the art gasoline fuel additive.
Adopt following non-limiting example to set forth the present invention.
Embodiment A-D
Under different temperature and duration of contact, be under the 4kg/kg at the ratio of catalyzer and oil, the fischer-tropsch products with the listed character of table 1 is contacted with the regenerated catalyst of heat.Catalyzer is the industrial FCC catalyzer of alumina-containing matrix and overstable zeolite Y, and described FCC catalyzer is available from the FCC unit of industrial operation.Zeolite Y content is 10wt%.Listed operational condition in the table 3.
Table 1
| Initial boiling point | 100℃ |
| Between 25-215 ℃ of following ebullient cut (wt%) | 46.8 |
| Between 215-325 ℃ of following ebullient cut (wt%) | 42.2 |
| Be higher than 325 ℃ of following ebullient cuts (wt%) | 11.0 |
Embodiment 1-4
As embodiment A-D, under different temperature and duration of contact, the fischer-tropsch products with the listed character of table 2 is contacted with the regenerated catalyst of heat.Use the catalyzer of the EXAMPLE III among the WO-A-9934917, obtain fischer-tropsch products according to example VI I.Listed operational condition in the table 3.
Table 2
| Initial boiling point | 280℃ |
| Has the cut wt% that is less than or equal to 10 carbon atoms | 0 |
| Has cut wt% greater than 30 carbon atoms | 80 |
| Has cut wt% greater than 60 carbon atoms | 50 |
| C 60+/C 30+ the ratio | 0.63 |
Table 3
| Experiment | Embodiment | Temperature (℃) | Duration of contact (s) |
| A | 1 | 500 | 4.06 |
| B | 2，5 | 525 | 0.7 |
| C | 3，6 | 525 | 4.06 |
| D | 4，7 | 625 | 0.7 |
Table 4
| Gasoline yield (wt%) (*) | Middle distillate productive rate (wt%) (* *) | Gasoline isoparaffin (wt% in the gasoline fraction) | Gasoline isoolefine (wt% in the gasoline fraction) | The positive alkene of gasoline (wt% in the gasoline fraction) | |
| A | -- | - | - | - | - |
| 1 | 74.00 | 11.06 | 31.04 | 36.96 | 18.09 |
| B | 52.58 | 35.88 | 2.93 | 8.00 | 14.27 |
| 2 | 52.90 | 13.27 | 17.10 | 50.15 | 25.83 |
| C | 68.70 | 13.63 | 15.59 | 16.93 | 8.14 |
| 3 | 70.29 | 5.91 | 8.64 | 62.90 | 26.06 |
| D | 53.86 | 26.24 | 4.67 | 21.47 | 18.54 |
| 4 | 46.12 | 7.43 | 14.48 | 40.21 | 31.99 |
(*) with gasoline fraction between 25-215 ℃ of following ebullient distillation fraction definition
(* *) is with the middle distillate between 215-325 ℃ of following ebullient distillation fraction definition.
According to table 4, can draw method of the present invention high gasoline yield will be provided.Gasoline fraction contains and obviously more helps high-octane compound.The method of prior art mainly is the product of n-paraffin, and it has obviously lower octane value.
Table 4 is further illustrated under the temperature of long duration of contact and relative gentleness, obtains high gasoline yield (embodiment 1 and 3).
Embodiment 5-7
Utilization has the condition of the fischer-tropsch products and the table 3 of the listed character of table 5, repeats embodiment 2-4.Listed the result in the table 6.
Table 5
| Initial boiling point | 100℃ |
| Has the cut wt% that is less than or equal to 10 carbon atoms | 14 |
| Has cut wt% greater than 30 carbon atoms | 62 |
| Has cut wt% greater than 60 carbon atoms | 39 |
| C 60+/C 30+ the ratio | 0.63 |
Table 6
| Embodiment | Gasoline yield (wt%) based on whole products | Gasoline isoparaffin (wt% in the gasoline fraction) | Gasoline isoolefine (wt% in the gasoline fraction) | The positive alkene of gasoline (wt% in the gasoline fraction) |
| 5 | 52.85 | 14.91 | 43.64 | 24.04 |
| 6 | 70.05 | 9.71 | 55.84 | 23.30 |
| 7 | 47.25 | 12.94 | 37.25 | 29.87 |
Embodiment 8
Repeat embodiment 6, just the part catalyzer is changed into the catalyzer that contains ZSM-5 of 25wt%.Based on whole catalyst charges, the catalyst based content of ZSM-5 is 20wt% (calculating based on whole catalyst weights).Gasoline yield is 47.99wt%.In gasoline fraction, isoparaffin content is 4.20wt%, and isoolefine is that 53.53wt% and positive alkene are 22.72wt%.With the productivity of propylene of embodiment 6 is that 4.85wt% (calculating based on whole products) compares, and productivity of propylene is 15.34wt%.
Embodiment 9
Repeat embodiment 2, just the part catalyzer is changed into the catalyzer that contains ZSM-5 of 25wt%.Based on whole catalyst charges, the catalyst based content of ZSM-5 is 20wt% (calculating based on whole catalyst weights).Listed the result in the table 7.
Embodiment 10
Repeat embodiment 3, just the part catalyzer is changed into the catalyzer that contains ZSM-5 of 25wt%.Based on whole catalyst charges, the catalyst based content of ZSM-5 is 20wt% (calculating based on whole catalyst weights).Listed the result in the table 7.
Table 7
| Embodiment | Based on the gasoline yield (wt%) of product (*) | Gasoline isoparaffin (wt% in the gasoline fraction) | Gasoline isoolefine (wt% in the gasoline fraction) | The positive alkene of gasoline (wt% in the gasoline fraction) |
| 2 | 52.90 | 17.10 | 50.15 | 25.83 |
| 3 | 70.29 | 8.64 | 62.90 | 26.06 |
| 9 | 55.88 | 37.75 | 21.79 | 19.37 |
| 10 | 45.76 | 0.83 | 65.62 | 27.53 |
| Iso-butylene productive rate (wt%) (*) | Trimethylmethane productive rate (wt%) (*) | N-butene (wt%) (*) | Productivity of propylene (wt%) (*) | |
| 2 | 2.08 | 1.41 | 2.82 | 2.77 |
| 3 | 2.72 | 0.86 | 3.33 | 4.73 |
| 9 | 4.77 | 2.17 | 6.10 | 13.89 |
| 10 | 7.84 | 3.42 | 9.78 | 16.45 |
(*) productive rate of all in the table 7 is all in gross product
The feasible raw material that can obtain to be used for alkylation step of high-load iso-butylene that table 7 explanation forms in this processing step and Trimethylmethane is to prepare pure isooctane especially according to known alkylation.
Claims (14)
1. the method for preparing aliphatic gasoline component, it carries out as follows:
(a) in riser reactor, under 450-650 ℃ temperature, between 1-10 under the duration of contact of second, with at the ratio of catalyzer and oil under 2-20kg/kg, fischer-tropsch synthesis product is contacted with the catalyst system that contains catalyzer, and wherein said catalyzer contains acidic matrix and large pore molecular sieve;
(b) from the product of step (a), separate gasoline fraction and the cut that contains Trimethylmethane and iso-butylene;
(c) make the Trimethylmethane and the iso-butylene that obtain in the step (b) carry out alkylation step, with the pentane of preparation trimethylammonium replacement; With
The product of the pentane that is rich in the trimethylammonium replacement that (d) obtains in gasoline fraction that obtains in the combination step (b) and the step (c).
2. the method for claim 1, wherein have in the employed raw material in the step (a) at least 60 or the weight ratio of the compound of more a plurality of carbon atoms and compound with at least 30 carbon atoms at least 0.2 and wherein at least the described compound of 30wt% have at least 30 carbon atoms.
3. the method for claim 2, wherein in the raw material of step (a) at least the described compound of 50wt% have at least 30 carbon atoms.
4. the method for claim 3, wherein in the raw material of step (a), have in the fischer-tropsch products at least 60 or the compound of more a plurality of carbon atoms be at least 0.4 with weight ratio with compound of at least 30 carbon atoms.
5. each method of claim 1-4, wherein the temperature of step (a) is lower than 600 ℃.
6. each method of claim 1-4, wherein acidic matrix is an aluminum oxide.
7. each method of claim 1-4, wherein large pore molecular sieve is the molecular sieve of faujusite (FAU) type.
8. each method of claim 1-4, wherein the catalyst system of step (a) also comprises zeolite beta, erionite, ferrierite, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23 or ZSM-57.
9. each method of claim 1-4, the fischer-tropsch synthesis product that wherein is used as raw material in step (a) obtains by the catalytic fischer-tropsch synthesis technique of cobalt.
10. the method for claim 9, wherein obtain described cobalt catalyst as follows: (aa) mix (1) titanium oxide or precursors of titanium oxide, (2) liquid and (3) cobalt compound to form mixture, wherein said cobalt compound is insoluble to small part in described liquid consumption; (bb) moulding and the dry mixture that so obtains; (cc) the calcining composition that obtains like this.
11. the aliphatic gasoline component that can obtain by each method of claim 1-10, it comprises greater than the compound of the trimethylammonium replacement of 90wt% and the mixture of the compound that monomethyl replaces, wherein the weight ratio of trimethylammonium compound and monomethylation compound is at least 0.03, and wherein said compound can be paraffinic hydrocarbons and alkene.
12. the gasoline component of claim 11, wherein the weight ratio of trimethylammonium compound and monomethylation compound is maximum 0.3.
13. the gasoline component of claim 11 or 12, wherein the content of pure isooctane is between 2-20wt%.
14. a Fuel Petroleum composition, it comprise claim 11-13 each aliphatic gasoline component, one or more additives, the aromaticity content of measuring by ASTM D5580-95, motor-method octane number between 1-22vol% greater than 90 and the sulphur content measured by ASTM D5453-93 be lower than 15ppmw.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2004/050931 WO2004106462A1 (en) | 2003-05-27 | 2004-05-26 | Process to prepare a gasoline |
| EPPCT/EP2004/050931 | 2004-05-26 | ||
| EP04106158.1 | 2004-11-29 |
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| CN1950488A CN1950488A (en) | 2007-04-18 |
| CN100575460C true CN100575460C (en) | 2009-12-30 |
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| CN102250651B (en) * | 2011-06-17 | 2014-07-09 | 西安聚德新能源技术有限公司 | Production process and device of large-proportion methanol gasoline for molecular sieve catalytic synthesis vehicle |
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| EP1359207A1 (en) * | 1998-03-26 | 2003-11-05 | Bp Oil International Limited | Fuel composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1359207A1 (en) * | 1998-03-26 | 2003-11-05 | Bp Oil International Limited | Fuel composition |
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