CN110050055A - Obtain method, renewable hydrocarbon stream and the gasoline preparaton for being suitable as the renewable hydrocarbon stream of gasoline preparaton component - Google Patents

Obtain method, renewable hydrocarbon stream and the gasoline preparaton for being suitable as the renewable hydrocarbon stream of gasoline preparaton component Download PDF

Info

Publication number
CN110050055A
CN110050055A CN201780066072.8A CN201780066072A CN110050055A CN 110050055 A CN110050055 A CN 110050055A CN 201780066072 A CN201780066072 A CN 201780066072A CN 110050055 A CN110050055 A CN 110050055A
Authority
CN
China
Prior art keywords
gasoline
hydrocarbon stream
preparaton
dehydration
sugarcane
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.)
Pending
Application number
CN201780066072.8A
Other languages
Chinese (zh)
Inventor
A·R·多斯桑托斯
W·R·吉尔伯特
E·J·德奥利韦拉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Brazil Petroleum Co
Original Assignee
Brazil Petroleum Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Brazil Petroleum Co filed Critical Brazil Petroleum Co
Publication of CN110050055A publication Critical patent/CN110050055A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
    • C10G3/55—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds
    • C10G3/57—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds according to the fluidised bed technique
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • 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
    • C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
    • C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
    • C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/22—Higher olefins
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a kind of methods, this method includes being dehydrated by fluid catalystic cracking to the byproduct by sugarcane ethyl alcohol, to obtain the renewable hydrocarbon stream being preferably mainly made of the alkene with 5 carbon atoms for gasoline, and it is related to thus obtained hydrocarbon stream and gasoline preparaton.

Description

Obtain the method, renewable for being suitable as the renewable hydrocarbon stream of gasoline preparaton component Hydrocarbon stream and gasoline preparaton
Technical field
The field of the invention
The present invention relates to the method for obtaining the renewable hydrocarbon stream for gasoline preparaton and thus obtained hydrocarbon streams and vapour Oily preparaton.
Background technique
Background of the invention
The arguement finally exhausted is naturally laid in about petroleum, and to emission level of the reduction from internal-combustion engine vehicle Demand has promoted the vehicle interesting not only to exploitation more efficiently, but also to the new environmentally compatible fuels of research and has urged It is interested to change converter.Therefore, it more and more continually requires to use renewable component in the links of fuel industry.
Recyclable fuel, also referred to as bio-fuel are the fuel of biological source.They by biomass (such as corn and soybean, Sugarcane, castor bean, rape, palm oil or hemp) it is made.
Using the advantages of bio-fuel with compared to the greenhouse gas emission that substantially reduces of fuel for being originated from petroleum and Source as renewable energy is related.The primary biological fuel being currently known is mainly by the alcohol (second of sugarcane and maize production Alcohol)；The biogas produced by biomass；Biological ether and biodiesel etc..Bio-fuel can be used individually in vehicle or and fossil Fuel mixing.
In above-mentioned bio-fuel, ethyl tert-butyl ether (ETBE) (ETBE) and ethyl alcohol are the products obtained by Brazil, and are The example for being widely used in the bio-fuel of gasoline preparaton.
Gasoline is substantially to be made of hydrocarbon and a small amount of (being added at distributor to it) for example pure and mild ether of oxygenatedchemicals Fuel.These hydrocarbon are usually aromatic hydrocarbons, alkene, cycloalkane and alkane, and usually than constituting those of diesel oil more " light ", because They are formed by the molecule with more short carbon chain (usually 5-10 carbon atom).
Depending on application, the content of oxygen-containing component limited by product specification, otherwise they will affect mainly with consumption and The related fuel performance of performance, this is attributed to oxygen-containing component lower energy content for hydrocarbon.
In addition to the hydrocarbon and oxygenatedchemicals, gasoline is also containing sulphur compound, nitrogenous compound and for numerous purposes Additive, wherein we can be mentioned that detergent and sediment monitoring additive.Therefore, the chemical composition of gasoline be it is complicated and It may change.In general, its boiling point is relatively low, this facilitates its use as fuel.In addition, its burning release it is extraordinary The energy of potential amount, and its price is economically feasible.
More particularly, automobile gasoline is generated by the various streams for being referred to as naphtha generated from various oil refining methods.According to The oil refining method for producing naphtha, different from each other in terms of the type and content of hydrocarbon of these naphthas contained by it, this is to make The reason of changing is constituted at gasoline.
Various methods can be used to obtain gasoline from petroleum.With the progress in engine design aspect, oil refining method is same When experienced continual differentiation.Change with the main design in terms of compression ratio for increasing power, refiner changes Into the manufacturing method of gasoline to meet the quality requirement for becoming increasingly harsher.At the same time, higher gasoline consumption has been Method through causing exploitation to give higher yield.These targets, which cause, constitutes most effective and one of complex technology oil refinery The status of industry.
For producing the main method of gasoline as fractionation, vacuum distillation, thermal cracking or catalytic cracking and catalytic reforming.
Widely used cracking is by fragmenting into the long hydrocarbon molecule of high molecular weight with its of shorter chain and lower molecular weight Its molecule is constituted.It is industrial extremely important method, allows to obtain tool for numerous purposes by single compound There are the various compounds compared with small molecule.
Cracking can be thermal cracking or catalytic cracking.Thermal cracking carries out at high temperature and pressure.For example, in order to by kerosene boiling range In molecule (diesel oil or lubricating oil) be converted into gasoline, used temperature is between 450 DEG C to 700 DEG C.However, due to using Catalyst, catalytic cracking do not need high temperature and high pressure, so that this method is safer and more economical.
In order to assess quality of gasoline, measurement is known as octane number (octane number) (also referred to as octane number (octane Rating property)) indicates the anti-knock compressed to fuel.
In octane scale, index 100 is attributed to isooctane (2,2, the 4- front threes that pinking only occurs under high compression ratio Base pentane；C8H18), and index zero is attributed to and issues the normal heptane (C of raw pinking in very low compression ratio7H16)。
When analyzing in model engine, it is different pungent that the octane number of gasoline informs that the anti-knock that the fuel possesses is equivalent to The anti-knock of the mixture of alkane and normal heptane, wherein the percent by volume of isooctane is numerically equal to octane number.For example, pungent The anti-knock that has of gasoline that alkane value is 80 is equivalent to the isooctane and 20% (volume/volume) of 80% (volume/volume) The anti-knock of the mixture of normal heptane.
Relationship between organic compound and octane number follows following rule:
Branched paraffin has octane number more higher than corresponding n-alkane；
Cycloalkane has octane number more higher than corresponding n-alkane；
Alkene has octane number more higher than corresponding alkane；
Aromatic hydrocarbons has very high octane number.
The octane number of gasoline is higher, and anti-knock is higher.Some components or even gasoline product have pungent on 100 Alkane value needs to determine octane number using other standards, such as the isooctane or known octane of the lead tetraethide of addition standard content The aromatic compounds of value.
Octane number is one of most important parameters of quality of gasoline, and directly related with the performance of product.However, other property It verifies critically important for performance, such as suitable volatile nature and using compatible burn rate and is enough to ensure that power With the energy content of independence.
Its all Optimal Parameters (such as octane number, burn rate and energy contents are combined in a kind of product and like products (calorific value)) the availability of gasoline stream be still from technology and from the challenge for business perspective.
Have it can be clearly seen that present needing exist for acquisition and originating in renewable raw materials from property in from the discussion above Energy angle sees the gasoline stream of more attracting property (especially more high heating value), to fill up by currently available renewable product The performance gap left such as oxygen-containing component (ethyl alcohol, ETBE etc.).
In this respect, the attention of R&D team has been directed to obtain these products from the biomass source of substitution, especially It is to upgrade byproduct from already existing method.
For example, fusel oil is the residue/byproduct obtained from alcohol fuel distillation factory, by more advanced alcohol (such as isoamyl Alcohol (IAA), isobutanol etc.) mixture constitute.These alcohol are classified as the congener of alcoholic fermentation, and must be in rectifying column Middle removing, because they tend to accumulate in a device.Be mass produced alcohol fuel country as Brazil in, using The alternative solution of the residue generated in this method will be to keeping ethyl alcohol production pollution less and more lucrative be of great significance. The low price of fusel oil and its isoamyl alcohol of high-content, in addition will demonstrate that exploitation needs every year in a large amount of fusel oil of Brazil's production It is correct for using the technology of this mixture.
Therefore, various files describe automobile gasoline for obtaining the renewable source for originating in these byproducts All methods as those mentioned above.However, not yet develop using the adaptability of oil Refining Technologies and use fusel oil or IAA as The method that raw material combines.
For example, file WO2013/169461 describes a kind of method for producing alkene and aromatic hydrocarbon, wherein will be comprising coming from The charging of the oil of biomass pyrolytic or its fraction is supplied to steam cracking factory at a temperature of 600-1000 DEG C, or in 900-1700 The counter-current reactor operated at a temperature of DEG C, and one or more hydrocarbon effluent fractions are produced by thermal cracking.However, splitting at this It is very economical and safe, and thus unattractive for meaning it not using high temperature and high pressure in change method.
File US2012/0220808A1 describe it is a kind of by the primary aliphatic alcohol of long-chain carry out liquid-phase dehydration react come with The method of high yield and highly selective production long-chain olefin.The term " liquid phase reactor " being such as used in the present invention indicates that reaction exists Not higher than being carried out at a temperature of raw alcohol boiling point, that is, not higher than there are still the temperature of liquid phase alcohol at a temperature of carry out.
It remains desirable, however, that developing a kind of method of renewable hydrocarbon stream for obtaining and being mainly made of light olefin for producing Gasoline with more attractive property in terms of performance perspective, particularly with more high heating value.
As by presenting in further detail below, the present invention is directed to the above-mentioned prior art is solved in a manner of practical and is effective The problem of.
Summary of the invention
General introduction of the invention
The present invention relates to a kind of use to be suitable as gasoline preparaton as raw material acquisition by the byproduct of sugarcane ethyl alcohol The method of the renewable hydrocarbon stream of component and thus obtained hydrocarbon stream and gasoline preparaton.The present invention limits in detail in the claims It is fixed.
According to present disclosure in a first aspect, providing a kind of obtain is suitable as the renewable of gasoline preparaton component The method of hydrocarbon stream, it is characterised in that this method includes one or more of: a) respectively in 350-550 DEG C and 0kgf/cm2 (0KPa)-2kgf/cm2Under the temperature and pressure of (196.13KPa), in the presence of optional powdered acid catalyst, it is based on Fluid catalytic cracking (FCC) technology carries out dehydration to the charging of the byproduct by sugarcane ethyl alcohol, wherein used to urge Agent/charge ratio changes between three and ten；And b) 20-70 DEG C, preferably 20-50 DEG C at a temperature of, to what is obtained in step a) Liquid product is distilled, and the hydrocarbon stream being mainly made of the alkene with 5 carbon atoms is obtained, wherein by the pair of sugarcane ethyl alcohol The conversion ratio of product to the alkene with 5 carbon is 80%-100%.
The liquid product obtained in step a) can be cooled before continuing distilation steps b).
It can be fusel oil by the byproduct of sugarcane ethyl alcohol, and more preferably isoamyl alcohol present in it.
The olefin stream obtained in step b) may include the iso-amylene percentage between 60%-80%.
The temperature of dehydration can be 450-500 DEG C.
The pressure of dehydration can be 1kgf/cm2(98.07KPa)-1.8kgf/cm2(176.52KPa)。
Powdered acid catalyst can be aluminium oxide, silica-alumina, zeolite Y and/or its mixture.
Catalyst/charge ratio can be between 4 and 8.
Conversion ratio by byproduct to the alkene with 5 carbon of sugarcane ethyl alcohol can be 90-100%.
According to the second aspect of the present disclosure, a kind of renewable hydrocarbon stream is provided, it is characterised in that the hydrocarbon stream is by such as The method that is discussed with reference to first aspect obtains.
Detailed description of the invention
This disclosure relates to a kind of byproduct used by sugarcane ethyl alcohol as raw material obtain for gasoline can be again The method of hydrocarbon stream.
Particularly, the disclosure is related to the method for obtaining renewable hydrocarbon stream, preferably by means of the pair by sugarcane ethyl alcohol The dehydration of product (especially fusel oil and more preferably isoamyl alcohol present in it), it is contemplated that these byproducts Brazil with Large-scale availability.The method is the cracking technology based on fluid catalystic cracking type (fluid catalytic cracking, FCC), It is allowed continuous in the gas phase using existing oil refinery equipment (being distributed using special purpose reactor) and prolongedly operates this method, To obtain the hydrocarbon stream being mainly made of the light olefin containing 5 carbon atoms.
Suitable and commercially available catalyst can be used in fluid catalystic cracking method, preferably includes powdered acid catalysis Agent, and more preferably aluminium oxide, silica-alumina, zeolite Y and/or these components any or all of mixture.? (it corresponds to charging (isoamyl alcohol or fusel oil) and catalyst circulation to catalyst/charge ratio used in the dehydration Weight flow rate) it can change between 4 and 8 between three and ten, preferably.
Reaction can carry out at a temperature of between 350-550 DEG C, preferably 450-500 DEG C.Operating pressure for reaction is The typical pressure of fluid catalystic cracking method (FCC), and can be in about 0kgf/cm2(0KPa) and 2kgf/cm2 Between (196.13KPa), preferably in 1kgf/cm2(98.07KPa) and 1.8kgf/cm2Change between (176.52KPa).
Selection aforesaid operations condition is to promote from the byproduct of sugarcane ethyl alcohol to mainly containing with 5 carbon atoms The maximum conversion rate of the hydrocarbon of branched-chain alkene (also referred to as iso-amylene).Meanwhile the reaction condition avoids the formation of time as octane number Grade product and have compared with low heat value come it is cracking and condensation byproduct such as liquefied petroleum gas (LPG) (3 and 4 carbon atoms) with And aromatic hydrocarbons such as benzene, toluene and dimethylbenzene.In general, the value of isoamyl alcohol to the conversion ratio with 5 carbon olefins is 80%-100%, it is excellent It is selected between 90%-100%, and generates good light naphthar.
It is preferred that the liquid product obtained from dehydration is cooling (prevent through evaporation loss iso-amylene), and then It is distilled at a temperature of between 20-70 DEG C, preferably 20 and 50 DEG C, in TBP (true boiling point (TBP)) tower, to separate naphtha cut.Such as Mentioned, the high conversion rate of isoamyl alcohol is higher than 80%.Other than other byproducts, this can be used as final result and provides one Kind of stream, the stream have the iso-amylene of 60-80% (w/w) percentage, high-octane rating and with for observed by automobile gasoline It is worth compatible stability.In addition, being originated from the content of sulphur present in the product of fusel oil and nitrogen compound to low miscellaneous including needing It is compatible that the various gasoline of the product of matter content evaporate section (segments of gasoline).
Therefore, compared with the other methods converted for biomass, dehydration distillation range needed for maximizing of isoamyl alcohol Yield and avoid in final fuel there are in terms of oxygenatedchemicals advantageously.
Specific embodiment
Following example illustrate various embodiments of the present invention.
Embodiment
Embodiment 1-produces iso-amylene stream with pilot-scale
The preliminary test that the operating condition for assessing FCC is carried out in unit is tried in the circulating cycle.Pilot scale unit is equipped with length The insulation riser and isothermal rectifier of 1 meter of degree and the regenerator by electric heating control temperature.The catalyst of the unit is hidden Amount is 2kg and feed flow rate is 1kg/h.The catalyst used is Ecat 1, a kind of Petrobras in gas oil-breaking The powdered catalyst containing zeolite Y of commercial FCC unit.Table I presents Ecat 1 catalyst and (and mentions further below Ecat 2) composition and catalyst specific surface area.
The composition and specific surface area of Table I, Ecat 1 and Ecat 2
Parameter ECAT 1 ECAT2
Specific surface area, m2/g 153 159.2
Al2O3, %w/w 41.8 43.2
Na, %w/w 0.33 0.23
Re2O3, %w/w 3.28 2.59
V, mg/kg 1284 544
Ni, mg/kg 1292 1053
P2O5, %w/w 1.00 0.75
Zeolite Y content 40% 40%
The influence of operating condition is studied using the charging of the isoamyl alcohol (IAA) in petrochemistry source, and is made in operation 3 Fusel oil is provided by ethanol distillation factory.
Table II presents the operating condition of pilot scale unit and the general introduction of iso-amylene yield, including cracking reaction temperature (TRX) And the ratio (CTO) of catalyst and charging (oil).Selection operation condition forms isoamyl to optimize the conversion ratio of IAA, by dehydration Alkene, and at the same time minimizing the formation with secondary octane number and the product compared with low heat value.The assessment of fusel oil processing is only in It is carried out under examination scale, emphasis is the lower raw material of assessed cost.Fusel oil used in operation 3 is contained based on dry matter 76% (w/w) IAA (71%3- methyl-1-butanol and 5%2- methyl-1-butanol), 6% (w/w) butanol and 16% (w/w) second Alcohol.In general, fusel oil contains the water of 17% (w/w), leads to the lower iso-amylene yield and higher compared with IAA is fed Water yield (operation 1 is than operation 3- Table II).In order to generate the liquid product of enough volumes, lasting operation in 3 hours is carried out.Liquid Product is collecting (prevent through evaporation loss iso-amylene) in the cooling container of dry ice, and then distills in TBP tower To separate naphtha cut (initial boiling point [IBP]=70 DEG C), about 1 liter of sample for being enough to complete characterization is generated.
Table II, the experiment condition tested for isoamyl dehydration of alcohols in pilot scale unit.
Table III gives the characterize data of the product generated in pilot scale unit after distillation, including low heat value (LCV) and high fever It is worth (HCV), and passes through the composition of gas-chromatography (GC) measurement.ASTM Test Method reference for each parameter is included in table In bracket in lattice first row.
It can be seen that from Table III, all fractions are all light enough, and there is low-density and high volatile (to pass through RVP- Randt (Reid) vapor pressure measurement), show that this method generates the stream with the property compatible with gasoline property.
About energy content, observe that the product for being originated from 99% fossil IAA of processing has the low heat value of about 44.3MJ/kg (LCV), this is the excellent value suitable for special gasoline preparaton.The LCV ratio of product from processing fusel oil is from IAA's The LCV of product low about 2.3%, and which reflects the relatively high ethanol contents (4.3%w/w) that there is recycling in distillation. It should be emphasized that processing fusel oil is proved to be promising, because the negative effect of the observed LCV to TBP fraction can lead to Final boiling point (FBP) (such as 50 DEG C) Lai Jiaozheng of distillation fraction is overregulated, this eliminates the presence (boiling point [BP]=78 of ethyl alcohol ℃)。
The product being dehydrated in Table III, pilot scale unit from 99% fossil IAA (operation 1 and 2) and fusel oil (operation 3) The characterize data of TBP distillation fraction (IBP-70 DEG C)
iFor IP value (alkylation products > 1200 point IP of 10%w/w component/90%w/w alkylation products mixture Clock)
iiBy being calculated by the composition data of GC
iiiThe RON of pure sample.Sample is very volatile, irregular combustion
ivFor 10%w/w component/90%w/w alkylation products mixture RON value (RON alkylation products= 98.5)
vFor 10%w/w component/90%w/w alkylation products mixture RON value (RON alkylation products= 96.4)
About octane number, it is impossible to measure the RON (research octane number (RON)) of net product, this, which is attributed to, upsets the fraction of analysis High volatile.The fraction for only carrying out self-operating 1 has the RON for being estimated as 99.4, shows that the stream has high-octane rating.Product Octane number assessment is with the alkylation products of every kind of stream and high isooctane content (80-85%w/w) with the mixed of ratio as follows Object is closed to carry out: the alkylation products of fraction and 90%w/w that 10%w/w is generated.With alkyl choline used in mixture Octane number is compared, and the RON octane number of mixture shows that all fractions have the similar performance of effect enhancing in the mixture.
About the stability of product, all fractions show that the value of existent gum and potential gum is compatible to for automobile gasoline Observed value.About induction period (IP), although the IP value of fraction is low, with the mixed of more stable stream (alkylation products) It closes the result obtained in object and wants much higher, illustrate that it is not problem.
Be worth it is specifically mentioned on the other hand, sulfur content and nitrogen content in the product from fusel oil to include need it is low It is compatible that the various gasoline of the product of impurity content evaporate section.These pollutants are not assessed in the fraction from 99% fossil IAA In the presence of because raw material used in test is not interested renewable raw materials.
Embodiment 2- produces biological iso-amylene stream with semi-industrial scale
With semi-industrial scale production iso-amylene stream equipped with 18m riser, insulation regenerator and the original for being insulated stripper It is carried out in type FCC unit.Table IV presents the operating condition for obtaining product.In order to provide IAA dehydration required energy, Burning torch oil, maintains the temperature of regenerator to be in designated value in the regenerator of unit.The catalyst inventory of prototype unit is 350 Kilogram.Before production test, the S10 diesel stream almost without sulphur is handled, to purge condenser system and guarantee the stream Sulfur content is lower than 10mg/kg.The IAA handled in half industrial FCC unit is from the fusel oil residue from sugarcane ethanol distillation Middle purifying (referred to as " biology-IAA ").Catalyst (Ecat 2) (being similar to catalyst used in embodiment 1) is by Petrobras Oil plant provides.Collect dehydrating prods and by means of density sensor in pressure vessel with 1kgf/cm2By the water of itself and generation Separation, this allows to monitor water-naphtha interface during vessel empty.Then the liquid product generated in FCC unit exists Fractionation is in distillation unit to generate final stream.Since it is derived from the product of plant origin raw material, so the product is referred to as " raw Object iso-amylene ".
Table IV (is transported for producing with the biological iso-amylene stream for being originated from 99% biology-IAA dehydration that semi-industrial scale obtains Row 1) operating condition.
Table V shows the data of the distillation fraction generated after 99% biology-IAA of characterization processing.
The product has the feature similar with the product obtained in pilot plant.About volatility, biological iso-amylene is found Product than generating in pilot plant is slightly light, and having higher RVP, the higher RVP is by relative to from pilot plant Product for light component (with 4 carbon compounds) the larger rate of recovery caused by.
Final products have high heating value and octane number (RON > 100 and LCV=44.8MJ/kg), and produce in pilot plant Fraction in the value observed it is compatible.Two kinds of properties be all it is excellent, illustrate that biological iso-amylene is for special gasoline preparaton Suitable stream.
Table V, dehydrating prods with semi-industrial scale from 99% biology-IAA iso-amylene stream (operation 1) characterize data
iFor IP value (alkylation products > 1.200 point IP of 10%w/w component/90%w/w alkylation products mixture Clock)
iiBy being calculated by the composition data of GC
iiiIt does not determine.Sample is very volatile, irregular combustion
ivFor 10%w/w component/90%w/w alkylation products mixture RON value (RON alkylation products= 98.5)
About stability, which has the behavior similar with the product of pilot plant, and need not use anti-oxidant add Add agent.In addition, it should be emphasized that, which is easier to produce, because not needing post-processing unit operation to ensure stability.
About the content of impurity (total N, total S and oxygen), low-down value is observed, this is for meeting all serial gasoline Any current specifications of (including with those of low sulfur content) will not cause any problem.
In general, the physical-chemical data (RVP, density, distillation, LCV and octane number) of the composition of product, biological iso-amylene and Stability data illustrates extraordinary applicability of the product as gasoline component, can provide needed for preparaton because it is used All properties.
In addition, the properties of biological iso-amylene are significantly better than for observed by the naphtha obtained as petroleum refining Property illustrates mainly to tend to be conducive to develop various special gasolines by the hydrocarbon stream that the alkene with 5 carbon atoms is constituted.
From above embodiments it is inferred that the dehydration of the byproduct by sugarcane ethyl alcohol of the FCC based on present disclosure Method leads to the hydrocarbon stream of the iso-amylene with high percentage, high-octane rating and energy content.The stability be directed to automobile gasoline Observed value is compatible, and to evaporate section to various gasoline compatible for the content of sulfur-bearing and nitrogenous compound.Therefore, which is suitble to For the various products (aviation gasoline, premium gas, competition gasoline) applied as exploitation has more preferable performance or as vapour The octane enhancing additive of vehicle gasoline.
Allow to fall into many variations in the protection scope of the application.The present invention is not limited to above-mentioned configuration/particular implementation sides Case.

Claims (14)

1. obtaining the method for being suitable as the renewable hydrocarbon stream of gasoline preparaton component, it is characterised in that this method comprises:
The charging of the byproduct by sugarcane ethyl alcohol is taken off using fluid catalytic cracking (FCC) in the presence of acid catalyst Water reaction,
Temperature and 0kgf/cm of the dehydration at 350-550 DEG C2(0KPa)-2kgf/cm2Under the pressure of (196.13KPa) Occur, and
Wherein the weight ratio of the catalyst/charging is between three and ten.
2. the method according to claim 1, further comprise 20-70 DEG C, preferably 20-50 DEG C at a temperature of to by the dehydration React obtained liquid product distillation.
3. method according to claim 2 further comprises obtaining the hydrocarbon stream being mainly made of the alkene with 5 carbon atoms.
4. according to the method in claim 3, wherein the byproduct by sugarcane ethyl alcohol to the alkene with 5 carbon conversion Rate is 80%-100%.
5. method according to claim 2, wherein producing the liquid obtained by the dehydration before continuing distillation Product are cooling.
6. according to the method for any one of preceding claims, wherein the byproduct by sugarcane ethyl alcohol is fusel oil, and More preferably isoamyl alcohol present in it.
7. according to claim 3 or the method for its any dependent claims, it is characterised in that described in being mainly made of alkene Stream includes the iso-amylene percentage of 60%-80%.
8. according to the method for any one of preceding claims, wherein the temperature of the dehydration is 450-500 DEG C.
9. according to the method for any one of preceding claims, wherein the pressure of the dehydration is 1kgf/cm2(98.07KPa)- 1.8kgf/cm2(176.52KPa)。
10. according to the method for any one of preceding claims, wherein the acid catalyst be aluminium oxide, silica-alumina, Zeolite Y and/or its any or all of mixture.
11. according to the method for any one of preceding claims, it is characterised in that the weight ratio of the catalyst/charging 4 and 8 it Between.
12. according to the method for any one of preceding claims, it is characterised in that by the byproduct of sugarcane ethyl alcohol to 5 carbon Alkene conversion ratio be 90%-100%.
13. renewable hydrocarbon stream is obtained by such as the method defined in any one of preceding claims.
14. gasoline preparaton, it includes the renewable hydrocarbon streams described in claim 13.
CN201780066072.8A 2017-11-15 2017-11-15 Obtain method, renewable hydrocarbon stream and the gasoline preparaton for being suitable as the renewable hydrocarbon stream of gasoline preparaton component Pending CN110050055A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/GB2017/053439 WO2019097199A1 (en) 2017-11-15 2017-11-15 Process for obtaining a renewable hydrocarbon stream suitable as a component of gasoline formulations, renewable hydrocarbon stream, and gasoline formulation

Publications (1)

Publication Number Publication Date
CN110050055A true CN110050055A (en) 2019-07-23

Family

ID=60627957

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201780066072.8A Pending CN110050055A (en) 2017-11-15 2017-11-15 Obtain method, renewable hydrocarbon stream and the gasoline preparaton for being suitable as the renewable hydrocarbon stream of gasoline preparaton component

Country Status (7)

Country Link
US (1) US20200270531A1 (en)
EP (1) EP3504296A1 (en)
CN (1) CN110050055A (en)
AU (1) AU2017436016A1 (en)
CA (1) CA3038764A1 (en)
PH (1) PH12019500667A1 (en)
WO (1) WO2019097199A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200133217A (en) * 2018-03-16 2020-11-26 토탈 마케팅 서비스 Preparation of olefins by alcohol dehydration, and their use for the production of polymers, fuels or fuel additives

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3969426A (en) * 1974-10-17 1976-07-13 Mobil Oil Corporation Conversion of methanol to products comprising gasoline boiling components
CN1508108A (en) * 2002-12-16 2004-06-30 北京美通科技发展有限公司 Combined process for synthesizing amylene alcohol
DE102009026586A1 (en) * 2009-05-29 2010-12-16 Evonik Oxeno Gmbh Preparation of 3-methyl-1-butene
US20130204058A1 (en) * 2010-08-03 2013-08-08 Total Research & Technology Feluy Combined process to make olefins from isobutanol
CN112166170A (en) * 2018-03-16 2021-01-01 道达尔销售服务公司 Preparation of olefins by dehydration of alcohols, and use thereof for the manufacture of polymers, fuels or fuel additives

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6437208B1 (en) * 1999-09-29 2002-08-20 Exxonmobil Chemical Patents Inc. Making an olefin product from an oxygenate
EP1892280A1 (en) * 2006-08-16 2008-02-27 BIOeCON International Holding N.V. Fluid catalytic cracking of oxygenated compounds

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3969426A (en) * 1974-10-17 1976-07-13 Mobil Oil Corporation Conversion of methanol to products comprising gasoline boiling components
CN1508108A (en) * 2002-12-16 2004-06-30 北京美通科技发展有限公司 Combined process for synthesizing amylene alcohol
DE102009026586A1 (en) * 2009-05-29 2010-12-16 Evonik Oxeno Gmbh Preparation of 3-methyl-1-butene
US20130204058A1 (en) * 2010-08-03 2013-08-08 Total Research & Technology Feluy Combined process to make olefins from isobutanol
CN112166170A (en) * 2018-03-16 2021-01-01 道达尔销售服务公司 Preparation of olefins by dehydration of alcohols, and use thereof for the manufacture of polymers, fuels or fuel additives

Also Published As

Publication number Publication date
US20200270531A1 (en) 2020-08-27
WO2019097199A1 (en) 2019-05-23
CA3038764A1 (en) 2019-05-15
AU2017436016A1 (en) 2019-05-30
PH12019500667A1 (en) 2019-07-24
EP3504296A1 (en) 2019-07-03

Similar Documents

Publication Publication Date Title
CN103189480B (en) The production of recyclable organism gasoline
Laksmono et al. Biodiesel production from biomass gasification tar via thermal/catalytic cracking
Cataluña et al. Specific consumption of liquid biofuels in gasoline fuelled engines
CN102482600A (en) Fuel oil base and aviation fuel composition containing same
CN108495913A (en) The method that high octane gasoline component is produced by the mixture of VGO and tall oil pitch
WO2012091815A1 (en) Integrated fcc biomass pyrolysis/upgrading
CN103975045A (en) Process for the production of gasoline by using butanol in the gasoline pool
Weber et al. Production of hydrocarbons from fatty acids and animal fat in the presence of water and sodium carbonate: Reactor performance and fuel properties
CN107922860A (en) Fuel formulations product
Wisniewski Jr et al. Upgrade of biofuels obtained from waste fish oil pyrolysis by reactive distillation
Mrad et al. Liquid hydrocarbon fuels from fish oil industrial residues by catalytic cracking
EP2940103A1 (en) A method for obtaining biofuels using ethanol, or mixtures of alcohol as biofuel or biocomponent and biofuel or biocomponent for the preparation of motor fuels
JP5639532B2 (en) C heavy oil composition and method for producing the same
Brown et al. What role for the bioeconomy in an electrified transportation sector?
US11674096B2 (en) Method of processing a bio-based material and apparatus for processing the same
Muraza Highlighting the greener shift in transportation energy and fuels based on novel catalytic materials
Speight Fuels for fuel cells
Lappas et al. Production of transportation fuels from biomass
Tracy et al. Gasoline production from phytol
CN110050055A (en) Obtain method, renewable hydrocarbon stream and the gasoline preparaton for being suitable as the renewable hydrocarbon stream of gasoline preparaton component
US10414992B2 (en) Fuel composition
Marlair et al. Booming development of biofuels for transport: Is fire safety of concern?
Palankoev et al. Optimization of Catalytic Cocracking of Vacuum Distillate and Bio-Oxygenates in the Presence of Zeolite ZSM-5 Using Two-Factor Regression Analysis
Baladincz et al. Expanding feedstock supplies of the second generation bio-fuels of diesel-engines
JP5403596B2 (en) Unleaded gasoline

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20190723