CN103384714A - Production of aromatics from renewable resources - Google Patents

Abstract

Renewable oils are converted to aromatics, by contact with a catalytically-active form of gallium, for use in the petrochemical industry and/or for fuel blending components or additives. The renewable oil(s) feature high oxygen content, high H/C mole ratios, and high fatty acid or fatty acid ester content prior to heating and contact with the catalyst. The catalyst may be, for example, a gallium-doped version of one or more zeolite- alumina matrix catalysts with pore sizes having 10 oxygen atoms in the pore mouth, such as ZSM-5, ZSM-11, ZSM-23, MCM-70, SSZ-44, SSZ-58, SSZ-35, and ZSM-22. Aromatics -production from the renewable oils is enhanced at higher gallium-cation levels, with the preferred level being about 1.0 Ga/framework-Al. While various renewable oils, or "bio-oils," may be used, algae oil has exhibited very high BTEX yields over the gallium cation catalyst, under conditions at or near 1 atm and approximately 400 degrees C.

Description

Prepare aromatic substance by renewable resources

Describe

The application requires the right of priority of the U.S. Provisional Application that is entitled as " preparing aromatic substance by renewable resources " 61/427,160 of submission on December 24th, 2010, and whole disclosures of this application are incorporated herein by reference.，

Technical field

The present invention relates generally to a kind of for prepare the method for aromatic substance from renewable resources.More specifically, preferred embodiment relates to and transforms the fatty of biomass derived or other contain lipid oils, as from naturally occurring non-dimension pipe photosynthetic organism body and/or from the oil of the non-dimension pipe photosynthetic organism body of gene modification; Rapeseed oil and derived from other oil of vegetables (as corn, soybean, sunflower and jowar); And/or from other plant, seed, fungi, bacterium and survival and the nearest oil of the other biological body of survival.

Background technology

Aromatic substance, particularly benzene, toluene, ethylbenzene and the dimethylbenzene (ortho position, a position and para-isomeride) that are commonly referred to " BTEX " or simpler " BTX " are chemical extremely useful in petrochemical industry.They have represented the structural unit such as the material of polystyrene, styrene butadiene rubbers, polyethylene terephthalate, polyester, Tetra hydro Phthalic anhydride, solvent, urethane, phenylformic acid and many other components.Usually, by for example in catalytic reforming or cracking refinery practice unit, separate by the BTX recovery unit afterwards and processing fossil oil petroleum fractions obtains BTEX to be used for petrochemical industry.

Patent documentation has been described and has been used for processing biological with the refining scheme of preparation transport fuel such as gasoline, jet and diesel oil.Referring to for example, the WO2008/103204 of the North Carolina State University that is entitled as " being the method for fuel with Wood Adhesives from Biomass " that on August 28th, 2008 announced.Also referring to, the people's such as Aravanis that are entitled as " method of refining hydrocarbon raw material " that on May 21st, 2009 announced open US2009/0126260, and the people's such as McCall that are entitled as " preparing aviation fuel by biological renewable raw materials " that announced on June 25th, 2009 open US2009/0158637.Yet patent documentation concentrates on from renewable raw materials and prepares transport fuel, rather than for the preparation of the aromatic substance of petrochemical industry.And, patent documentation concentrates on mainly by the renewable raw materials of Triglycerides, be for example vegetables oil (as rapeseed oil, soybean oil, false flax oil and Jatropha oil) and the animal tallow (as beef is fatty, mutton is fatty and chicken fat) of about 100% triglyceride level.

Need to prepare from renewable resources the technology of the aromatic substance of high yield.Especially, need to can replace the BTEX of petroleum derivation for " the green aromatic substance " of polymkeric substance, plastics, medicine, clothes, synthetic rubber, dyestuff, solvent and other consumption and Industrial products in petrochemical industry.Need to be from this " the green aromatic substance " of algal oil, described algal oil have than the vegetables oil of high triglyceride and animal tallow complexity the composition of Duoing.

Summary of the invention

The present invention includes for one or more renewable oils are converted into aromatic substance, for example to be used for petrochemical industry and/or to be used for the blend components of fuel or method, catalyzer and/or the equipment of additive.Working method of the present invention comprises makes one or more renewable oils contact with the gallium of catalytic activity form, for example contacts with the catalyzer of the gallium that comprises the catalytic activity form (at this paper also referred to as " the gallium modification " catalyzer).The catalyzer of this gallium modification can comprise zeolite or other solids of the gallium (for example as the gallium positively charged ion) that keeps the catalytic activity form.The present invention can comprise the product that makes by described method.

Described one or more renewable oils can be available from biomass, and described biomass are defined as material survival or that survive in 50 years in the past, or comprise the material of the described material of significant quantity.The example of this renewable oils is rapeseed oil and derived from other lipid base bio oil of vegetables (as corn, soybean, sunflower and jowar); From naturally occurring non-dimension pipe photosynthetic organism body and/or from the oil of the non-dimension pipe photosynthetic organism body of gene modification, and/or from the oil of other plant, seed, fungi, bacterium and other biological body.Bio oil can be extracted from their biomass separately by routine techniques.As used herein, the non-dimension pipe of term photosynthetic organism body includes but not limited to macro, microalgae and cyanobacteria (blue-green algae).

In certain embodiments, described one or more renewable oils are characterised in that greater than 1.5 the H/C molar ratio of (1.7-2.1 usually), and approximately 1 to the about oxygen level of 35wt-% (5-15wt% usually).Described renewable oils comprises a large amount of lipid acid or fatty acid ester, comprises the glyceryl ester (as monoglyceride, triglyceride and/or triglyceride level) of free fatty acids and/or lipid acid.H/C molar ratio, oxygen level can be depending on for example source and/or the technology of extracting and/or the preprocessing before the catalyzer with the gallium modification contacts of renewable oils with free fatty acids in described one or more renewable oils and the relative quantity of glyceryl ester from biomass.Fatty acid part can be for example approximately 4 to about 30 carbon atoms, but is generally 10 to 25 carbon atoms, and even is more generally as 16 to 22 carbon atoms.The most normally, fatty acid part is saturated, or contains 1,2 or 3 two key.Some embodiment of renewable oils contains at least some as the triglyceride level of the glyceryl ester of C16-C22 carboxylic acid, and therefore can contain the C50+ compound, yet, when being heated to high temperature, the C-16-C-22 component that the many triglycerides in renewable oils and/or triglyceride level resolve into them.Renewable oils also can comprise other materials, as carotenoid, hydro carbons, phosphatide, simple fatty acids and their ester, terpenes, sterol, Fatty Alcohol(C12-C14 and C12-C18), tocopherol, polyisoprene, carbohydrate and/or protein.

High hydrogen/carbon ratio due to some embodiment of renewable oils, and the dehydrogenation functionality of the catalyzer of some gallium modification, therefore expect that some embodiment of the present invention produces a large amount of hydrogen, described hydrogen can be fed to the hydrogen consumable unit in refining, for example hydrotreater or hydrocracking device.Therefore, some embodiment of the present invention can be used for " green " BTEX preparation and the preparation of " green " hydrogen.

In certain embodiments, it is the shape selection material that gallium keeps solid, and more generally, described solid is zeolitic material, and wherein in cationic exchange, in the heart at least some are filled by gallium.In certain embodiments, gallium keeps solid and is one or more zeolites of the gallium doped forms in the aperture that has 10 Sauerstoffatoms in the aperture-alumina base body catalyst, for example ZSM-5, ZSM-11, ZSM-23, MCM-70, SSZ-44, SSZ-58, SSZ-35 and ZSM-22.The inventor finds, improved from renewable oils to prepare aromatic substance under higher gallium level, one of them level be Ga occupy the positively charged ion site at least 90%, and replaced by Ga before the proton at those places, positively charged ion site or other positively charged ions.Exemplary gallium level is 90-100% positively charged ion site is replaced by Ga, and this is referred to herein as " 1.0Ga/ skeleton-Al ".

Catalyzer in some embodiment of the present invention can have the above gallium loading level of 1.0Ga/ skeleton-A1, that is, gallium exists to equal the 100% above amount of positively charged ion replacement.In this case, will there be super skeleton (extraframework) Ga, namely corresponding to more than the amount of 1Ga/ skeleton-A1 and be arranged in zeolite hole or the Ga on the outside of crystallization of zeolites particle.

Although usually use the zeolite of silica-alumina form, zeolite framework can contain other metals, such as gallium, boron, iron, phosphorus, germanium, indium etc.The zeolite framework that contains other metals can be suitable for preparing the catalyzer of gallium modification, for example is used for the gallium of filling cationic form with the catalyzer as some embodiment of the present invention.

Solid can pass through catalyst field technique known to the skilled (for example, using the first wet impregnation method of the zeolite of the gallium compositions that is dissolved in the water) and be adapted to keep gallium.Method for the preparation of the catalyzer of gallium doping also is described in U.S. Patent No. 4,727, and in 206,4,746,763,4,761,511 and 5,149,679, the instruction of described patent is incorporated herein by reference.

Described one or more renewable oils can comprise " whole crude " (i.e. whole oil extracts of authigenic material), and/or one or more cuts of described whole crude.Described one or more renewable oils have carried out the whole crude/cut of preprocessing before can being included in and being fed to the gallium catalyst process.For example, in this context " preprocessing " can comprise come unstuck, before technique that RBD (refining known in the art, bleaching and deodorization), hot-work, hydrotreatment and/or be fed to comprises the catalyzer that uses the gallium modification deoxidation or with the renewable oils improvement to a certain degree other techniques.And in certain embodiments, described one or more renewable oils can processing (" co-fed ") be to aromatic substance preparation technology of the present invention altogether with other oil, and described other oil are as fossil oil/cut.

The inventor thinks, many embodiment of the present invention can carry out in conventional refinery practice equipment, be used for the existing unit of fossil oil or the existing unit of transformation namely fully, perhaps based on the fossil petro-technology but for the new unit of renewable oils optimum construction.Contacting described one or more renewable oils can carry out in multiple flow scheme and refining unit, includes but not limited to single reactor or series connection flow reactor, and randomly removes liquid phase between reactor before gas phase flows to downstream reactor; Fix or " filling " catalyst bed; Fluid catalyst beds; And/or moving-bed.For example, be used for described existing, the transformation of some embodiment of the present invention or new unit can comprise with following same or similar those: fluid catalytic cracking (FCC) unit (for example referring to Figure 23), UOP CCR ^TMCyclar ^TMUnit (for example referring to Figure 24), UOP CCR Platformer ^TM, naphtha reformation fixed-bed reactor or other fixed-bed reactor unit, all these all are derived from the fossil petro-technology.Described FCC unit has been designed for from oil and has prepared gasoline component, comprises with respect to higher octane component benzene being produced reach minimum so that octane to reach maximum those FCC unit.Described UOP CCR ^TMCyclar ^TMThe unit is to be designed for to use the gallium catalyzer from the moving catalyst continuous catalyst regeneration unit of oil C3 and C4 feed preparation aromatic substance.Described UOP CCR ^TMPlatformer ^TMThe unit is to be designed for the moving catalyst continuous catalyst regeneration unit for preparing high octane gasoline from naphtha, and usually uses platinum catalyst to be rich in the liquid product of aromatic substance with preparation.Described fixed bed catalyst unit is also known in the refining field, for example, is designed for from naphtha and prepares gasoline component, and usually use platinum or rhenium catalyst to be rich in " half regeneration " reformer of the liquid product of aromatic substance with preparation.

The technique unit that the renewable oils of high per-cent is fed to based on the fossil petro-technology can make the equipment of reactor/standpipe reaction zone upstream and operation adapt to because above-mentioned fossil oil unit all not special design be used for described renewable oils raw material.Yet, the product stream from high per-cent renewable oils operation is more likely effectively processed in the equipment in the reaction zone downstream in these unit and operation, because usually be similar to the product that is rich in aromatic substance of said units from the BTEX product of this embodiment.A possible exception is, may need to change to process H2O, CO and/or the CO of some renewable oils that derives from elevated oxygen level in the equipment in reaction zone downstream or operation.Selectively or additionally, before being fed to described reaction zone, the preprocessing that is used for the deoxidation of renewable oils can prevent excessive water generates and hydrogen consumption at described reaction zone.

The technique unit that the renewable oils of low per-cent is fed to based on the fossil petro-technology can be desirable selection, particularly due to only be expected in several years next can less described one or more renewable oils that measure.Therefore, the common processing of described one or more renewable oils and other raw materials may be required and/or favourable, thereby produces the technique unit of the catalyzer of " part charging " described one or more renewable oils and " part filling " gallium modification.Can be described one or more renewable oils although " fully charging " means the approximately 100wt% (for example 99-100wt%) of the raw material of technique unit at this paper, term " part charging " means still less at this paper that the raw material of per-cent can be described one or more renewable oils.Be the catalyzer of gallium modification (for example gallium cationic catalyst) although " fully filling " means the approximately 100wt% (for example 99-100wt%) of the catalyzer of technique unit at this paper, term " part is loaded " means still less that per-cent is the catalyzer of gallium modification.

Be used for this part filling and part feed operation optimization operational condition (comprising the condition that raw material contact from catalyzer) can with this paper after to load those operational conditions of advising with complete charging example fully different.For example, may need for the higher temperature of high space velocity or fluidized-bed or moving-bed condition more.In this case, for example, the raw material-contact temperature of catalyst of optimization can be up to 600 ℃, but more generally can be in 450-550 ℃ of scope.Based on data disclosed herein and the data that can be used for from the purifier of fossil petroleum operations, those skilled in the art can optimize the condition of this part filling and part feed operation and need not undo experimentation.

In certain embodiments, described one or more renewable oils can be fed or the unit of co-fed catalyzer to containing at least some gallium modifications before carry out preprocessing.For example, preprocessing step can comprise thermal treatment and/or the hydrotreatment of renewable oils or its cut.For example, expection comprises hydrotreatment or comprises thermal treatment and the processing scheme of the algal oil of hydrotreatment afterwards produce to be used for the desirable charging of FCC unit or co-fed.Perhaps, comprise the thermal treatment of a part of algal oil (for example last running of algal oil) and renewable oils afterwards through heat treated and also can produce for the desirable charging of FCC unit or co-fed without the processing scheme of the hydrotreatment of heat treated cut.

Embodiments of the invention need not be confined to said units or processing selection altogether.Other machining cells, flow scheme and/or other common raw materials can provide collaborative or favourable result.

Description of drawings

Figure 1A is the schematic diagram of the laboratory reaction device system of the single reactor of use used in the experiment of example I, III and IV,

Figure 1B is the schematic diagram of used in the experiment of example II laboratory reaction device system, and described laboratory reaction device system comprises two reactors of series connection, and is adapted to remove product liquid between reactor.

Fig. 2 is the figure from the weight percent yield of the product liquid (trilateral) of the test SAP275-279 on HZSM-5 catalyzer (without gallium) in example I and steam product (square), it has shown that increasing temperature has reduced the productive rate of product liquid, and has increased simultaneously the amount of steam product.

Fig. 3 is for the experiment SAP281-283 in example I, the figure of the steam product productive rate that changes along with the gallium (from left to right) of the amount of the increase that is added into catalyzer, and it has shown propane and the ethane that changes along with the gallium that increases especially.Molecule in the figure account for from all steam products of each experiment～98%.0.0Ga result be the mean value of SAP284-287, " error bar " shown 95% fiducial interval.

Fig. 4 is that the productive rate (circle) of the productive rate (square) of productive rate (trilateral), steam product of product liquid in the experiment SAP281-283 of example I and the coke on catalyzer is with respect to the figure of the gallium loading level of the increase of catalyzer.Along with the gallium content that increases, liquid yield (trilateral) increases, and it is almost constant that coke (circle) keeps, and steam product (square) reduces.The mean value of SAP284-287 (without Ga) is used for zero gallium content in the figure.

Fig. 5 is for the various gallium loading levels in example I (increasing from left to right), the figure of the boiling point distribution of organic phase product.The major part of product falls in 60-188 ℃ of scope.

Fig. 6 is the figure of benzene productive rate, toluene productive rate, ethylbenzene yield, dimethylbenzene productive rate and total BTEX productive rate in example I, and it has shown that the BTEX productive rate increases along with the gallium content of ZSM-5 catalyzer.

Fig. 7 be in example III on GaZSM-5 (rod on the left side) and HZSM-5 catalyzer (rod on the right), by the figure of the steam product productive rate that obtains 400 ℃ of lower algal oil crackings.

Fig. 8 be in example III on GaZSM-5 catalyzer (rod on the left side) and HZSM-5 catalyzer (rod on the right), by under 400 ℃ on catalyzer algal oil cracking and the figure of the independent BTEX component productive rate that obtains, total BTEX productive rate and gasoline yield.

Fig. 9 is the figure of the gas-phase product that produces in the gas oil cracking process in example IV.

Figure 10 derives from the BTEX of gas oil cracking (example IV) and the figure of gasoline yield for BTEX and gasoline yield than the cracking that derives from algal oil (example III), and both are all under 400 ℃.

Figure 11 is the simulation distil curve than the algal oil of example III, the figure of the simulation distil curve of the Conoco Phillips gas oil of example IV, comprising maximum gasoline boiling point curve for your guidance.

Figure 12 is the figure of simulation distil of gas oil product (example IV), algal oil product (example III) and the rapeseed oil product (example I) of cracking separately experiment.

Figure 13 is that the transformation efficiency % of the algal oil charging of example V and vacuum gas oil samples is with respect to the figure of catalyst/oil ratio.

Figure 14 is that the coke wt% of the algal oil charging of example V and vacuum gas oil samples is with respect to the figure of transformation efficiency.

Figure 15 be in example VI the algal oil charging, through the transformation efficiency % of the algal oil of hydrotreatment and the vacuum gas oil figure with respect to the catalyst/oil ratio.It should be noted that this figure comprises the algal oil charging that is added into Figure 13 and the algal oil data through hydrotreatment of vacuum gas oil data.

Figure 16 be in example VI the algal oil charging, through the coke wt% of the algal oil of hydrotreatment and the vacuum gas oil figure with respect to transformation efficiency.It should be noted that this figure comprises the algal oil charging that is added into Figure 14 and the algal oil data through hydrotreatment of vacuum gas oil data.

Figure 17-22 are respectively the algal oil charging of example VI, through the wt% productive rate of gasoline, LCO, DCO, TC2, TC3 and the TC4 of the algal oil of hydrotreatment and the vacuum gas oil figure with respect to transformation efficiency %.

Figure 23 is the schematic diagram of an example of the conventional fluidized catalyst conversion unit (FCC) that can be adapted to operate in certain embodiments of the present invention.

The conventional UOP CCR of Figure 24 for being adapted to operate in certain embodiments of the present invention ^TmCyclar ^TMThe schematic diagram of an example of unit.

Embodiment

Referring to the following detailed description that comprises example I-IX and relevant form and accompanying drawing, have described but be not the embodiment of only method of the present invention, equipment and product.

The inventor thinks, roughly predicted what happens in commercial from the data of the laboratory scale experiment of example I-VII.For example, the data in example I-III have predicted that roughly the packed bed gallium cationic catalyst that has fully filling, complete fully-charged renewable oils (comprising rapeseed oil and algal oil), the charging-catalyzer under about 1.0WHSV (weight hourly space velocity) contact and be controlled at the operation of the temperature of (for example 400 ℃) in 350-450 ℃ of scope.Data in example IV have predicted that roughly therefore, example IV can be used for predicting the performance difference between renewable oils and gas oil on the catalyzer of selected gallium modification and the fossil oil gas-oil feed of processing under the condition from example I and III.Data in example V and VI have roughly been predicted respectively algal oil and through the FCC of the algal oil of hydrotreatment processing.Data in example VII have roughly been predicted the thermal treatment of some algal oil, described thermal treatment be as subsequently improve by hydrotreatment and use the fluid catalytic cracking of catalyzer of gallium modification before the preprocessing step.

The experimental data of example I-III has been supported some embodiment, wherein renewable oils is able to effective processing on the catalyzer of gallium modification, and obtained simultaneously the extremely favourable result of aromatic substance and hydrogen preparation, wherein randomly, gas oil also can be able to effective processing (example IV) on the catalyzer of identical gallium modification.In example I-IV in gallium cationic catalyst data and example V and VI the combination of FCC data supported some embodiment of the present invention, wherein algal oil is improved by preprocessing step and the fluid catalytic cracking afterwards (randomly using oil as co-fed) of hydrotreatment, and wherein the FCC catalyzer comprises additional gallium cationic catalyst and prepare aromatic substance further to improve from algal oil in described fluid catalytic cracking.In example I-IV in gallium catalyst data, example V and VI the combination of the thermal treatment data of FCC data and example VII supported some embodiment of the present invention, wherein algal oil is improved by the preprocessing step of thermal treatment and hydrotreatment and FCC fluid catalytic cracking afterwards (randomly using oil as co-fed), and wherein the FCC catalyzer comprises additional gallium cationic catalyst and prepare aromatic substance further to improve from algal oil in described fluid catalytic cracking.

In certain embodiments, one or more renewable oils and other oil co-fed (or " part charging "), the wherein catalyzer of the charging of combination contact gallium modification.Broad range of the present invention can be included in any renewable oils of processing any amount in the operation of the catalyzer that uses the gallium modification, comprise by solvent extraction, by as above HTT technology or other biological matter processing/extractive technique and available from the cut of those and they of biomass, wherein renewable oils is any per-cent of whole raw materials.For example, one or more renewable oils can consist of contain the gallium positively charged ion keep catalyzer the unit raw material be low to moderate approximately 1wt%, but due to by catalyzer with have a shown large BTEX benefit of renewable oils, the inventor expects that renewable oils finally consists of the major portion of whole raw materials of selected technique unit, for example, in certain embodiments, the 5wt% at least of whole raw materials of technique unit, at least 10wt%, at least 50wt-% at least 80 or 90wt-% can be described one or more renewable oils.Therefore, in such an embodiment, renewable oils is in the scope of 5-100wt%, 10-100wt%, 50-100wt-% of raw material, in 80-100wt% or 90-100wt% scope for the raw material of one or more selected unit.In certain embodiments, first being processed is used for can being selected from the component of described one or more renewable oils blend on the catalyzer of gallium modification: fossil oil, oil, C3-C4, naphtha, gasoline, rocket engine fuel, diesel oil, gas oil, heavy gas oil and their arbitrary combination.Add altogether man-hour in the FCC unit, the expection renewable oils can be processed altogether with for example gas oil/vacuum gas oil.At Cyclar ^TMAdd altogether man-hour in the unit, the expection renewable oils can be processed altogether with for example C3-C4.

Some charging processing and implementation example altogether also comprises together with other catalyzer (for example with the non-catalyzer that contains gallium) catalyzer that loads/feed the gallium modification of (" part filling " operation) to the unit.The catalyzer of gallium modification can consist of any per-cent of catalyst loading/stream.For example, the catalyzer of gallium modification can consist of the approximately 1wt% that is low to moderate of catalyzer in technique unit, but due to by catalyzer and the shown large BTEX benefit of renewable oils, the inventor expects the 5wt% at least of the whole catalyzer in the final Component units of catalyzer, 10wt%, 50wt%, 80wt% or 90wt% at least at least at least at least.Therefore, in such an embodiment, the catalyzer of gallium modification is in 5-100wt%, 10-100wt%, 50-100wt%, 80-100wt% or the 90-100wt% scope of whole catalyzer.It should be noted that, term in this paper and claims " catalyzer of gallium modification " generalized definition is any solid that comprises the gallium of catalytic activity form, and they can be including but not necessarily limited to other examples of the catalyzer of the zeolite of gallium cationic catalyst, gallium doping and gallium modification herein.

For example, in the fluid catalytic cracking unit, the expection renewable oils can part be fed to the FCC unit together with gas oil or other petroleums.In such an embodiment, an only part that is fed in whole raw materials of FCC technique unit is renewable oils, for example, all raw materials be less than 99wt%, more may 1-20wt% or 5-10wt%.In such an embodiment, expection gallium cationic catalyst is the additive/fill-in of the catalyst stream of FCC unit, and the catalyst stream of described FCC unit is comprised of acid zeolite FCC catalyzer (as zeolite y) usually basically.In such an embodiment, all the only part in catalyst loadings/fillings (stream) is the catalyzer of gallium modification, for example whole catalyst loadings/stream less than 99wt%, more likely 1-20wt% or 5-10wt%.The FCC catalyzer will be regenerated in the revivifier part of FCC unit with the gallium cationic catalyst together.Can regulate temperature of reaction in this case, optimizing the overall performance based on the mixture of the catalyzer in the unit and charging, and the anticipation reaction temperature is for example approximately in the scope of 400-555 ℃.

Needn't require catalyst make-up or change so that described one or more renewable oils are fed to UOP Cyclar ^TMThe unit is because this unit uses the gallium cationic catalyst to be used for transforming C3 and C4 raw material usually.Equally, be expected at Cyclar ^TMCatalyst regeneration in the unit is effectively, because Cyclar ^TMCCR ^TMRegeneration section is designed for and the similar gallium cationic catalyst of those catalyzer of some embodiment of the present invention.Therefore, due to existing Cyclar ^TMUnit filling gallium catalyzer also is adapted to the gallium catalyzer, and therefore possible is with renewable oils or the renewable oils of part together with C3 and C4 charging or other chargings are fed to Cyclar completely ^TMOr similar unit.

Although UOP CCR is Platformers ^TMOr fixed bed naphtha reformer reactor can be the candidate unit of some embodiment of the present invention, but can notice that expection gallium cationic catalyst does not need usually at Platformers ^TMReclaiming process with the required relative complex of platinum-reforming catalyst used in many other naphtha reformers.Some gallium cationic catalyst can by the coke combustion step and after on catalyzer in the process of treated oil (namely therein at the renewable oils temperature of processing on catalyzer and in environment) reduction regenerated.Therefore, as the only oxidation regeneration part in the FCC unit or simple batch oxidation rather than as at UOP CCR Platformer ^TMIn oxidation used and special reducing process and equipment afterwards, can be effective to the regeneration of some catalyzer of the present invention.In some embodiment that provides in the fixed-bed catalytic reformer, for example, a filling gallium cationic catalyst in expection series connection flow reactor, and the conventional reforming catalysts of other reactor charge, and be adapted to reactor and the therefore independent regeneration of the catalyzer of a plurality of types.

In example I-IV, the protonated form of Zeolite/alumina base catalyst used can be described to the simplest form of Zeolite/alumina base catalyst, and proton is filled at the cationic exchange center in its mesolite fully.Each cationic species is relevant to aluminium atom in mixing zeolite framework.Therefore, the ratio that can say the skeleton-Al of proton and protonated form is 1/1, and described form is called " HZSM-5 " (" H " or " H more strictly ⁺" be proton), wherein ZSM-5 represents " supersiliceous zeolite-5 " (Substituted Mordenite (mordenite framework inverted) of structure type MFI-reversing).

Make the Zeolite/alumina base catalyst of gallium used in example I-IV filling form, wherein the gallium level is called as the mark in the positively charged ion site that is replaced by gallium.Make the catalyzer that the Ga level equals 1.0Ga/ skeleton-Al, 0.33Ga/ skeleton-Al and 0.10Ga/ skeleton-Al.In these materials, Ga replaces proton.Therefore, for the 1.0Ga/ skeleton, nearly all positively charged ion site is occupied by Ga, and nearly all proton is replaced by Ga.Therefore, " 1.0Ga/ skeleton-Al " catalyzer can be described to have the positively charged ion site that is occupied by Ga of 90%-100%, or the positively charged ion site that is occupied by Ga of 95-100%.For other Ga fillings, only a part of proton is replaced by Ga.In some forms, use term " 0Ga/ skeleton-Al ", this means to be replaced by Ga without proton, and this is equivalent to be called " HZSM-5 " (or " complete protonated form " catalyzer).Exemplary catalyzer has gallium as positively charged ion, and it has compensated the anion frame of zeolite.The many embodiment that it may be noted that catalyzer of the present invention are not the acid type zeolites, and described acid type zeolite comprises gallium rather than aluminium in skeleton.

Described the gallium catalyzer and be used for that particularly C2, C3 and C4 prepare aromatic substance from short chain fossil oil hydrocarbon.U.S. Patent No. 4,727,206 disclose and are used for having methane as main ingredient and have the gallium catalyzer of the raw material of the optional ethane that is contained in raw material and C3-C6.U.S. Patent No. 4,746,763 disclose the gallium catalyzer that is used for processing C2-C6 aliphatic cpd.U.S. Patent No. 4,761,511 have described the catalyzer for the preparation of aromatic substance, and propose the C2-C12 paraffinic hydrocarbons and can be used as raw material, but this patent instruction C2-C8 paraffinic hydrocarbons is preferred raw material, and the C2-C4 paraffinic hydrocarbons is particularly preferred raw material.U.S. Patent No. 4,766,265 disclose from ethane (C2) preparation liquid aromatic compound.U.S. Patent No. 4,855,522 have mentioned the gallium catalyzer that is used for processing C2-C12 compound, but concentrate on the C5-C7 paraffinic feed.U.S. Patent No. 5,149,679 have mentioned the C2-C12 raw material, but preferred C2-C6, particularly preferably C2-C4 raw material.UOP Cyclar ^TMThe unit has used some in the catalyzer of mentioning in these patents to be used for C3 and C4 raw material.Therefore, the gallium cationic catalyst is known, and the technician of catalytic field will understand how to prepare this catalyzer.

Yet, the inventor thinks, prior art does not have teaching to use this gallium catalyzer from renewable oils (particularly have a large amount of C12+ compounds, a large amount of C16-C22 lipid acid/ester chain and/or even a large amount of C50+ compounds those) preparation aromatic substance and/or preparation hydrogen.The renewable oils that this gallium catalyzer is applied to comprise oxygen containing biological compound (as lipid acid, triglyceride level, aldehyde, ketone, ester and/or alcohol etc., described oxygen containing biological compound is present in naturally occurring vegetables oil with significant quantity) is not to be apparent.The inventor thinks, this gallium catalyzer that is designed for and is applied to the C2-C4 raw material is applied to from renewable oils, particularly from rapeseed oil or algal oil prepares BTEX and/or preparation hydrogen is unexpected and non-obvious.

The renewable crude oil of present disclosure can be by variety of way from extracting the biomass of survival in 50 years in the past.For example, rapeseed oil used is commercially available rapeseed oil in the experiment of example I and II, and it is known oil available from Semen Brassicae campestris.Again for example, renewable algal oil used is the example of the kind of the renewable oils that can extract from naturally occurring non-dimension pipe photosynthetic organism body and/or from the non-dimension pipe photosynthetic organism body of gene modification by variety of way in the experiment of example III-V.The non-dimension pipe photosynthetic organism body of gene modification can be for example for to change chloroplast(id) and/or the nuclear gene group part of algae with interested gene.As used herein, the non-dimension pipe of term photosynthetic organism body includes but not limited to algae (it can be macro and/or microalgae).The term microalgae comprises, for example little algae (as little Sphaerellopsis (Nannochloropsis sp.)), cyanobacteria (blue-green algae), diatoms and dinoflagellates (dinoflaggellate).Thick algal oil can be available from the algae of described naturally occurring or gene modification, wherein control or change growth conditions (for example salinity of nutrient level, light or medium) obtaining required phenotype, or obtaining that certain lipid forms or lipid a complete set of (lipid panel).

In certain embodiments, biomass substantially go up and are algae, for example surpass the algae of 80wt%, or surpass the algae of 90wt%, or the algae of 95-100wt% (dry weight).Interested especially algae bio matter is included in the light compositing algae that grows in light.Yet other embodiment can comprise that there be not algae bio matter or other " boarder's object (the host organism) " that grows under light in acquisition.For example, in some cases, boarder's object can be the photosynthetic organism body of growth in darkness, is perhaps to weaken or to destroy the organism of mode gene modification of the light compositing ability of organism.Under this growth conditions, when boarder's object can not light compositing when (for example owing to lacking light and/or gene modification), usually, the nutrition of necessity is offered organism to support growth under light compositing not existing.For example, the organism substratum of (or on it) growth therein can be replenished any required nutrition, comprises organic carbon source, nitrogenous source, phosphorus source, VITAMIN, metal, lipid, nucleic acid, micro-nutrients and/or organism particular demands.Organic carbon source comprises that boarder's object can metabolic any carbon source, includes but not limited to acetic ester, simple carbohydrates (for example glucose, sucrose and lactose), complex carbohydrates (for example starch and glycogen), protein and lipid.Be not that all organisms can both make the metabolism of specific nutrition, and this nutrition mixture can be modified to another kind of organism from a kind of organism, so that suitable nutrition mixture to be provided.Those skilled in the art will understand the suitable nutrition mixture of how to confirm.

In certain embodiments, the algae that can extract suitable oil is Chlamydomonas (Chlamydomonas sp.), for example Chlamydomonas reinhardtii (Chlamydomonas reinhardtii.), Dunaliella (Dunaliella sp.), Scenedesmus (Scenedesmus sp.), chain band Trentepohlia (Desmodesmus sp.), Chlorella (Chlorella sp.) and little Sphaerellopsis (Nannochloropsis sp.).can comprise that synechococcus belongs to (Synechococcus sp.) from its example that obtains the cyanobacteria of suitable crude oil, Spirullina (Spirulina sp.), synechocystis (Synechocystis sp.), artrospira spirulina (Athrospira sp.), proto green algae (Prochlorococcus sp.), chromosphere Trentepohlia (Chroococcus sp.), Gleoecapsa sp., hidden ball Trentepohlia (Aphanocapsa sp.), aphanothece belongs to (Aphanothece sp.), Merismopedia (Merismopedia sp.), Microcystis (Microcystis sp.), chamber ball Trentepohlia (Coelosphaerium sp.), former green Trentepohlia (Prochlorothrix sp.), Oscillatoria (Oscillatoria sp.), Trichodesmium (Trichodesmium sp.), Microccoleus (Microcoleus sp.), Chroococcidiopisis sp., Anabaena (Anabaena sp.), Aphanizomenon (Aphanizomenon sp.), post born of the same parents Trentepohlia (Cylindrospermopsis sp.), cylinder spore Trentepohlia (Cylindrospermum sp.), Tolypothrix (Tolypothrix sp.), thin sheath Ulothrix (Leptolyngbya sp.), Lin Shi Trentepohlia (Lyngbya sp.) or Scytonema (Scytonema sp.).

Algae preparation and extractive technique are known in the art, comprise algal grown and the extraction of gene modification, and some embodiment of the present invention comprise the thick algal oil raw material/cut from any growth and extractive technique.Can gather and dry algae, then extract oil from lysing cell or destruction cell.But the cell chemical cracking perhaps can destroy cell walls with mechanical force.With an organic solvent (as hexane) extracts oil from cracking/destruction cell.Algal oil used in example III extracts from algae bio matter for the use hexane, the oil of then processing by conventional RBD technique (as for that known technique of vegetables oil field of food).Algal oil in example III first being processed in zeolite catalyst cracking technique is not carried out hydrotreatment, reformation or cracking.

Obtain the selectable technology of thick algal oil from biomass

Some embodiment comprises by comprising the step that is different from solvent extraction or comprising the thick algal oil that the technology of the step except solvent extraction obtains.For example, some embodiment is included in the hydrothermal treatment consists of solvent extraction (for example by heptane, hexane and/or the MIB) biomass before of thick algal oil, and subsequently pass through processing without the embodiments of the invention of RBD processing.Therefore, after extracting and before some improved technology of the present invention, some algal oil raw material does not stand any RBD processing (conventional known and be used for refining, bleaching and the deodorizing technology of high triglyceride bio oil), does not stand the independent step of any refining, bleaching or deodorization yet.

Some embodiment of described hydrothermal treatment consists comprises acidification step.Some embodiment of hydrothermal treatment consists comprises that heating is (for clear, at this paper also referred to as " being heated to the first temperature "), cooling and acidifying biomass, be to reheat and the separating and remove solvent to obtain oleaginous composition from organic phase of solvent interpolation, organic phase and water afterwards.Before pre-treatment step optionally adds to the step that is heated to the first temperature, wherein said pre-treatment step can comprise biomass (being generally biomass and the water composition of following steps (a)) are heated to pretreatment temperature (or pretreatment temperature scope) lower than described the first temperature, and approximately keep for some time under the pretreatment temperature scope.The first temperature usually approximately 250 ℃ to the about scope between 360 ℃, as shown in hereinafter listed step (b), and pretreatment temperature usually approximately 80 ℃ to the about scope between 220 ℃.In certain embodiments, can be approximately 5 minutes to approximately between 60 minutes in the hold-time under the pretreatment temperature scope.In certain embodiments, can add acid in the pre-treatment step process, for example to reach approximately 3 biomass-water composition pH to about 6 scopes.It should be noted that hydrothermal treatment consists and solvent extraction process can be used as intermittent process, successive processes or anabolic process and carry out.

Some embodiment of hydrothermal treatment consists and solvent extraction operation (HTT) can comprise:

A) obtain to comprise the waterborne compositions of described biomass and water;

B) described waterborne compositions is heated to approximately 250 ℃ in closed reaction vessel to about the first temperature between 360 ℃, and in the time that keeps at described the first temperature between 0 to 60 minute;

C) waterborne compositions of (b) is cooled to envrionment temperature and the about temperature between 150 ℃;

D) waterborne compositions through cooling of (c) is acidified to approximately 3.0 to less than 6.0 pH, to produce the composition through acidifying;

E) composition through acidifying of (d) is heated to approximately 50 ℃ to about the second temperature between 150 ℃, and keeps described composition through acidifying approximately 0 to approximately between 30 minutes at described the second temperature;

F) volume is approximated greatly the composition through acidifying that is added into (e) at the solvent of the volume of described water in the composition of acidifying, to produce the solvent extraction composition, wherein said solvent is slightly soluble in water, but oily compound dissolves in described solvent at least basically;

G) described solvent extraction composition is heated to approximately 60 ℃ in closed reaction vessel to about the 3rd temperature between 150 ℃, and keeps approximately 15 minutes to about time between 45 minutes at described the 3rd temperature;

H) described solvent extraction composition is separated into organic phase and water at least;

I) remove organic phase from described water; And

I) remove solvent from described organic phase, to obtain oleaginous composition.

The composition of the thick algal oil (" the thick algal oil of HTT ") that obtains by as above hydrothermal treatment consists and solvent extraction techniques can be different from the composition of the algal oil (as the algal oil in example III) that solvent extraction and RBD process, and some embodiment of the present invention can comprise described one or more renewable oils, and described one or more renewable oils comprise the thick algal oil of described HTT or its cut, basically by the thick algal oil of described HTT or its fractions consisting or by the thick algal oil of described HTT or its fractions consisting.

Following example has illustrated some embodiment of method described herein, wherein than the catalyzer of non-gallium modification, contacts by the catalyzer with the gallium modification and has realized the significantly more BTEX of high yield.Example has illustrated embodiments of the invention, and make embodiments of the invention become possibility, but method of the present invention, device and/or catalyzer are not necessarily limited to details wherein, and for example, the algal oil except those algal oils of example is contained in broad scope of the present invention.And various reactors and product reclaim structure, gallium to be kept catalyst composition, catalyst/oil ratio, catalyzer-raw material duration of contact, feed stock conversion, temperature and pressure (comprise describe in detail those other) and is contained in broad scope of the present invention in example.The technician in refining operation field will understand how described technology is applied to the business refining operation after reading and inspecting present disclosure, to realize substantial benefit as described herein.

Example

The example summary

Example I-III has described the processing of in using a plurality of tests of (comprising that protonated form and gallium positively charged ion keep the catalyzer of form) of zeolite-alumina base body catalyst rapeseed oil or algal oil in detail.Test has shown the good productive rate from the BTEX of rapeseed oil and algal oil, particularly when using the gallium form, and shown BTEX productive rate and/or the productive rate trend that to use some other renewable oils (comprising those renewable oils from other plant, non-dimension pipe photosynthetic organism body, vegetables, seed, fungus and bacterium source) and obtain.

Example IV has described in detail and has kept the processing of fossil oil gas oil on catalyzer from the selected gallium positively charged ion of example I-III, compares with result from renewable oils processing being used for.

Example V and VI have described in detail than fossil oil vacuum gas oil, process the algal oil of algal oil and hydrotreatment by fluid catalytic cracking, and have described some embodiment that wherein FCC catalyst make-up has the catalyzer of gallium modification.

Example VII described by thermal treatment, processed algal oil by hydrotreatment and fluid catalytic cracking subsequently, and described some embodiment that wherein FCC catalyst make-up has the catalyzer of gallium modification.

Example VIII has described an exemplary FCC technique unit of commercial applications, and it comprises the CONSTRUCTED SPECIFICATION of fluidized-bed and is used for the composition/make-up catalyst of described fluidized-bed and the system of additive.

Example IX has described the technique unit of an exemplary specific construction of commercial applications, and it can be similar to UOP Cyclar ^TMThe unit, and be designed for the raw material that is basically formed by renewable oils or formed by renewable oils fully.

The analysis of example charging

The rapeseed oil of example I and II is the commercially available oil available from Semen Brassicae campestris, and it contains the C18 of about 60-70wt-%: 1 and the about oxygen of 12wt%.

The algal oil of example III has the type of analyzing as following table 1-3.Can notice the free fatty acids of 48.8wt-%, wherein 45.5wt-% is C18: 1 free fatty acids (carbon chain lengths=18, monounsaturated).A part in free fatty acids in this algal oil can be in algae naturally occurring those, and a part can be in the process of extracting the lipid acid of " release " from the glyceride compounds of lipid acid from algae.Also notice the algal oil oxygen level of 10.52wt%.

The thick algal oil analysis (% by weight) of table 1.

The general composition of the thick algal oil of table 2.

The general analysis of the thick algal oil of table 3.

As above HTT step a-j acquisition is passed through in the algal oil charging of testing in example III-VI or quoting, and describes in as following table 4-6.

The charging of table 4. cut quality %-algal oil

The summary of table 5. compounds category-algal oil charging

Table 6. ultimate analysis-algal oil charging

The experimental installation summary

Example I and III use the reactor assembly 10 of the 20g scale of schematic representation in Figure 1A.Described reactor assembly is by LabVIEW ^TMProgram and the national DAQ of instrument company hardware are controlled.For the experiment of using rapeseed oil, double-piston chromatogram pump 12 is the extraction thing from the flask 14 of raw material, and it is pumped in the stove 16 that contains reactor 18.For the algal oil experiment, fresh feed pump is the ISCO piston pump with 500cc capacity, and it can process highly viscous algal oil.Do not use raw material preheating stove 20, because determine that before it is with the rapeseed oil thermally splitting before rapeseed oil arrives catalyzer.Reactant mixes before the top that enters reactor 18 with through the nitrogen gas stream 22 of heating.Reactor under the nitrogen that mixes and reactant flow and by catalyst bed 24.Reactor effluent is through cooling worm 26 and liquid trap 28, and cooling worm 26 and liquid trap 28 all are contained in ice bath 30.Leave liquid trap through cooling steam, and through miniature GC32, then arrive outlet.The miniature GC of Agilent2804 measured the composition of gas phase in every 4 minutes.

Reactor 18 in example I and III is the stainless steel reaction pipe of 1/2 inch diameter, and it is 24 inches long, and contain stove 18 " 10g catalyst bed 24 placed in the middle in the heating zone.The granulated glass sphere 40 support catalyst beds that reactor bottom is filled help to make the charging evaporation at the granulated glass sphere 42 on described catalyst bed before charging arrives catalyzer.In preparation work, use the preheating oven of raw material can cause the rapeseed oil thermally splitting before rapeseed oil can arrive catalyzer, therefore do not use raw material preheating stove 20 in the experiment in example I-III.

Axially insert two thermopairs in the catalyst zone of tubular reactor measures bottom 2 inchs below the top and catalyst bed in example I and III more than the temperature of 2 inchs.Thermopair also is installed in the heating space of stove.LabVIEW ^TMThe base sequence of control is regulated furnace, makes the mean value of top and bottom catalyst temperature remain on setting point.Same program is control pump and gas flow controller also, and records simultaneously all temperature and flow.Programmable Chromtech ^TMDouble-piston pump is supported the flow of 0.001 to 12.00mL min, although the vegetable seed oil viscosity is limited in pump the flow that is no more than about 1mL/min and counterpressure is not provided.The ISCO pump that is used for sending algal oil is programmed for sends 0.001 to 204cc/min charging.A pair of Brooks instrument company (Brooks Instruments) mass flow controller series connection running is accurately to provide the nitrogen flow of 10SLM at the most.This single reactor system and use thereof further describe in following example I.

Measurement then from the aqueous phase separation organic phase, and is measured the quality that remains water from the quality of the product liquid of each experiment in example I and III.When catalyst charge shifts out from reactor, use small sample to estimate coke content in the microbalance system, then the remainder with used catalyst is placed in horizontal pipe furnace, with by under 575 ℃ at 80/20Ar/O ₂Middle burning 4 hours and regenerating.Will be before and after regeneration the percentage difference between catalyst quality as actual coke content, this and the microbalance measurement matched well of coke content.Each total steam product of reporting of experiment represents the estimation of measuring based on the miniature GC that in time gaseous product forms.Form data integration in time, to obtain the total amount of each gaseous product.

Example II uses improved reactor assembly (being schematically shown as Figure 1B) comprising two reactors of series connection, and removes liquid between two reactors.Each in two structure of reactor of example II, reactor charge, temperature control, product condensation and product stream measurement and analysis are substantially the same with aforesaid device and the method for single reactor example I and III.This two reactor system and use thereof further describe in following example II.

Example IV use with example I and III in those substantially similar or identical equipment and operation used, as understanding by reading example IV.Example V uses equipment and the operation of FCC MAT test, and equipment and the operation of example VI use hydrotreatment and the test of FCC MAT afterwards, as understanding by reading these examples respectively.

Example I: the catalytic cracking of rapeseed oil on GaZSM-5

The catalytic cracking of rapeseed oil is carried out on the HZSM-5 zeolite catalyst (hereinafter referred to as " GaZSM-5 ") of gallium doping in the reactor assembly of 20g scale.The purpose of this experiment is to optimize the particularly formation of benzene, toluene, ethylbenzene and dimethylbenzene (BTEX) of aromatic substance, to be used for the fuel blend or as the raw material of chemical industry.Be used for other zeolites of cracking rapeseed oil than the inventor, for example than zeolite-β, when at the upper cracking rapeseed oil of the ZSM-5 (also claiming HZSM-5) of protonated form, observed BTEX and the light paraffins of high yield.After the cracking experiment that rapeseed oil is contacted with HZSM-5, the similar cracking experiment that the inventor makes rapeseed oil contact with GaZSM-5 is with the purpose for further increase BTEX productive rate.Good BTEX productive rate obtains in the GaZSM-5 experiment, and described productive rate is significantly higher than those productive rates that use protonated forms of zeolite to obtain.The inventor thinks, the catalyzer of gallium doping will formed light paraffins effectively be converted into aromatic substance in cracking process, also the high-carbon array of renewable oils divided simultaneously to be converted into BTEX.The inventor thinks, due to the ability of dehydrogenation of gallium, so the catalyzer of gallium doping increased the alkene generation, and catalyzer with the C16-C18 chain dehydrogenation of renewable oils and cracking to less alkene, particularly C5+ alkene.Due to the shape selective of catalyzer, so these C5+ alkene are cyclized into C5 and C6 ring compound subsequently, and described C5 and C6 ring compound are further converted to aromatic substance.Therefore, it is believed that when the processing renewable oils, the high BTEX selectivity of catalyzer is partly because light paraffins transforms, and importantly at first is not cracked into C2-C4 because long-chain is converted into BTEX.In this group experiment, than the 32.3%BTEX that cracking rapeseed oil on HZSM-5 produces, the cracking rapeseed oil produces 39.3%BTEX on GaZSM-5.And GaZSM-5 is reduced to 0.25% with the ethane productive rate by 3.1%, and propane yield is reduced to 14.6% from 21.8%.

Experiment

The HZSM-5 of gallium doping makes with 1/10,1/3 and 1/1 Ga/ skeleton-A1 ratio, this means the positively charged ion site about 1/10,1/3 or all hold the Ga positively charged ion.In the situation of the Ga/ skeleton 1/10 and 1/3-Al ratio, remaining positively charged ion site still holds proton.The first step of catalyzer preparation is to form pill from Powdered HZSM-5, and described Powdered HZSM-5 is catalyst based available from the Mobil ZSM-5 of molecular sieve catalyst international corporation (Zeolyst Intemational) with powder type.This is by using Zeolyst CBV5524G powder (50/1SiO ₂/ A1 ₂O ₃) and complete described Zeolyst CBV5524G powder and 20wt%A1 ₂O ₃In conjunction with and be extruded into 1/16 " pill and the calcining.The proton content of this material uses the program temperature desorption of Tri N-Propyl Amine to measure, and discovery has 61/1 actual SiO ₂/ A1 ₂O ₃Ratio (for the method, referring to V.Kanazirev, K.M.Dooley, G.Price, J.Catal.146 (1994) 228-236).Then, be dissolved in 4.77g Ga (NO in 22.97g water by use ₃) ₃XH ₂O just 25g batch of wet dipping the HZSM-5 pill and make 1/1GaZSM-5, wherein determine that by the microbalance drying experiment x is about 9-11.Moistening catalyzer under 120 ℃ in baking oven dried overnight.Use respectively 1.52 and 0.51g Ga (NO ₃) ₃XH ₂O makes 1/3 and 1/10 catalyzer in a similar fashion.Before catalytic cracking, Ga/HZSM-5 is at mobile N ₂In be heated to 500 ℃ (they being oxide compound with nitrate transformation), then under 30% hydrogen stream in nitrogen of 100mL/min under 500 ℃ the activation.The ion-exchange of Ga positively charged ion and proton in known reactivation process acceleration zeolite.

Rapeseed oil in the upper cracking of HZSM-5 material (that is, without gallium), can produce maximum BTEX with definite which temperature under 350,400,450 and 500 ℃.The cracking result is presented at has maximum BTEX under 400 ℃, so the GaZSM-5 experiment is also carried out at this temperature.

Following the carrying out of cracking experiment:

A) the 10g zeolite catalyst is filled in reactor;

B) 10g borosilicate glass pearl is poured over the zeolite top;

C) reactor is packed in stove;

D) set up N ₂Stream;

E) for containing the Ga material, make reactor reach activation temperature, then catalyzer is activated;

F) make reactor reach the cracking temperature;

G) in cracking process, use the co-fed 0.0465SLM of nitrogen (also being used for dry catalyst before reaction);

H) beginning rapeseed oil charging, 0.182mL/min (being equivalent to WHSV=1); And

I) reaction-ure feeding total amount, 10g

Based on the difference between the grams of the product of the grams of reaction-ure feeding and collection, the total mass balance of carrying out each experiment.The product of collecting is divided into three parts: 1) gaseous product, it is by the continuously measured of miniature GC system, 2) product liquid of condensation, it is collected from the effluent of reactor in the trap of 0 ℃ of lower constant temperature, and 3) stay the coke on catalyzer.Measure the quality of condensed fluid product, then from the organic phase water phase separated, and analyze organic phase by simulation distil and GC-MS.When the catalyst charge that consumes shifts out from reactor, use small sample to determine coke content in the microbalance system.Then use the O in Ar ₂The synthetic gas that forms makes the remainder of the catalyzer of consumption stand coke in calcining furnace and removes.The miniature GC that the gaseous product that carries out in time by integration forms measures, and uses known N ₂Flow is determined whole steam products of recovery as interior mark.

Productive rate calculates with weight percent (wt-%), is defined as Y=100x PF/RC, and wherein Y equals the productive rate in % by weight, and PF equals the weight of formed product, and the weight of the RC reactant that equals to transform.100 transformation efficiencys of oily reactant are provided due to the operational condition that select to be used for experiment in all examples, and therefore the RC in as above equation is identical with the reactant that is fed to reactor assembly.

Usually, account for 98% of reactant as the weight balancing in following table 7.As described shown in Figure 2 from the result of the preliminary experiment SAP275-279 on HZSM-5 catalyzer (without gallium), the productive rate of product liquid (trilateral) reduces along with the temperature that increases usually, and gaseous product (steam product, square) the opposite trend of demonstration, namely usually increase along with the temperature that increases.The not considerable change along with temperature of the productive rate of solid product.

The reaction conditions of table 7. example I and mass balance (reactant in each experiment is 10 grams)

As seen Fig. 3 is added into HZSM-5 (experiment SAP281-283) with gallium and has effect more significantly, approximately 2 times of temperature variation.Than the mean value of experiment SAP284-287, gallium has increased liquid yield, has reduced simultaneously gas yield.The steam product productive rate changes along with the amount of the increase of the gallium of the catalyzer that is added into experiment SAP281-283, particularly for propane and ethane.Molecule shown in Figure 3 account for from all steam products of each experiment～98%.0.0Ga result be the mean value of SAP284-287, " error bar " shown 95% fiducial interval.

As shown in Figure 4, mean value than SAP284-287 (without Ga), increasing Ga content (SAP281-283) has increased the productive rate (trilateral) of liquid, and coke (circle) maintenance is almost constant, and the amount of steam product (square) reduces.

Product analysis

In gas-phase product (referring to Fig. 3), along with Ga content increases, propane yield is reduced to 14.6% from 21.8%.Similarly, the ethane productive rate is reduced to 0.25% from 3.1%, and the hydrogen productive rate increases to 1.2% from 0.3%.

Although test to prepare aromatic substance rather than gasoline, the inventor has still characterized product liquid by simulation distil.This is shown in Fig. 5 of the boiling point distribution of having described the organic phase product.The great majority of product fall in 60-188 ℃ of scope, and this is typical for the ZSM-5 catalyzer of main preparation BTEX.

The gasoline-range material is the cut in boiling below 225 ℃.Gasoline requires the fuel of (D4814) regulation 10%, 50%, 90% and 100% to seethe with excitement at some temperature, is called T10, T50, T90 and FBP (final boiling point).FBP is fixed on 225 ℃, but the seasonal ground of other temperature and different regional.These temperature provide the breakpoint for the composition of estimating organic phase product liquid shown in Figure 5.The known BTEX for the preparation of high yield of HZSM-5, it all has the boiling point in 60-188 ℃ of scope.Yet aspect BTEX prepared, the catalyzer performance of gallium doping significantly was better than HZSM-5, and productive rate as shown in Figure 5 confirms.When Ga/ skeleton-Al increased to 1.0 by 0, the productive rate of the product between 60-188 ℃ increased to 40.8% by 34.6%, in the rapeseed oil that transforms.

As shown in Figure 6, product liquid is also analyzed with quantitative BTEX content by GC-MS, and described BTEX content increases along with the gallium content of ZSM-5 catalyzer.When Ga/ skeleton-Al increased to 1.0 by 0, benzene (B.P.80.1 ℃) productive rate increased to 8.4% from 7.5%, and consisted of the material in most 60-93.5 ℃ scope.Toluene (B.P.110.6 ℃) performance is similar, and has maximum productive rate and change, by 15.4% until 19.3%.It also consists of the material in the 93.5-188 ℃ of boiling spread that only surpasses half.Along with the gallium content that increases in catalyzer, C8 aromatics yield (ethylbenzene, B.P.136 ℃; P-Xylol, B.P.138 ℃; M-xylene, B.P.139 ℃; O-Xylol, B.P.144 ℃) also increase to 11.6% by 9.5%.

For 1.0Ga/ skeleton-Al material, 7.0 percentage points of total BTEX gain in yield make BTEX consist of 77.3% of organic liquid product.The aromatic substance heavier than C8 cut is present in organic liquid phase, but these more are difficult to quantitatively, and usually more cheap than BTEX cut.

Example I conclusion

Known HZSM-5 catalyzer can prepare high-caliber benzene, toluene and dimethylbenzene.Application standard HZSM-5 catalyzer cracking rapeseed oil produces approximately 32.3% BTEX under 400 ℃, but by gallium is added into catalyzer, and the inventor finds, BTEX gain in yield 7wt-% under the same conditions reaches approximately 39.3%.These BTEX aromatic substance consist of 77% of organic liquid product, therefore, except the possible renewable source that has represented the aromatic substance that is used for chemical industry, also described BTEX aromatic substance directly might be blended in kerosene or diesel oil, to obtain almost identical with JetA-1 rocket engine fuel.Need other test to measure the primary character of rocket engine fuel from the product of these experiments, as zero pour, vapour pressure, viscosity, flash-point and the combustion heat.

Example II: two reactors by series connection are catalytically conveted to aromatic substance with rapeseed oil

Use two reactors of series connection to carry out rapeseed oil to the catalyzed conversion of aromatic substance.The operation purpose of this example is to optimize valuable to gasoline or as the formation of benzene, toluene, ethylbenzene and the dimethylbenzene (BTEX) of chemical.Rapeseed oil cracking on H-ZSM-5 shown and produced a large amount of light paraffins, and the feed oil of 25wt% for example is as shown in example I.This example is by increasing light paraffins to the conversion of BTEX, and the inventor thinks by long-chain is converted into BTEX, thereby continues to be intended to obtain the experiment of " green BTEX " preparation.In this example, use the multiple reactor system, the steam product that wherein comes comfortable H-ZSM-5 or GaZSM-5 to go up the main reactor of cracking rapeseed oil is fed to the secondary response device that contains GaZSM-5, and is converted into BTEX.In this reactor assembly, " master " means the first reactor of oily raw material charging, and " inferior " means the second reactor from the gas/vapor effluent charging of main reactor.

Contain BTEX productive rate that the secondary response device of GaZSM-5 will obtain at cracking rapeseed oil on H-ZSM-5 (in the first reactor) and be increased to 43.8wt% by the oily charging of 39.5wt%, be i.e. the gain in yield of 4.3wt-%.The BTEX productive rate that the secondary response device that contains GaZSM-5 also will obtain at cracking rapeseed oil on GaZSM-5 (in the first reactor) is increased to 51.2wt% by the oily charging of 46.3wt%, i.e. the gain in yield of 4.9wt-%.Be also noted that the BTEX productive rate (46.3wt-% and 51.2wt-%) that obtains all is significantly higher than the BTEX productive rate (39.5wt-% and 43.8wt-%) that obtains when being the gallium catalyzer after protonated catalyzer when two reactors all contain the catalyzer of gallium doping.

Catalyzer

Use the cracking experiment of the ZSM-5 catalyzer of protonated form to use to have the Zeolyst H-ZSM-5 of 25/1 Si/ skeleton-A1 ratio.Use the experiment of Ga cracking catalyst also to use identical Zeolyst H-ZSM-5 material, by Ga (NO ₃) ₃First wet interpolation and the gallium that loads is the loadings of 1Ga/ skeleton-Al.Term " GaZSM-5 (1-1) " is used for emphasizing that loadings is 1Ga-1Al.

Experiment

Cracking process carries out in the double-reactor structure that two reactors by the series connection shown in Figure 1B form.Two reactors are all vertically installed in stove.Thermopair is placed in the middle in each reactor tube, with the temperature in the monitoring catalyst bed.This temperature is regarded as temperature of reaction, and remains on constant setting point by the LabVIEW base sequence of control of regulating stove power.From product liquid condensation in glass cylinder of the first reactor (11mm I.D., and 521mm overall length), steam product enters the second reactor (11mm I.D., and 419mm overall length) to be used for further reaction.From product liquid condensation in glass cylinder of the second reactor, steam product flows to the miniature GC (Agilent G2804A) of every four minutes analytical gas compositions.

the details of the two reactor system 10 ' of Figure 1B is following draws: nitrogengas cylinder 51, gas regulator 52, valve 53, quality controller 54, syringe pump 55, first (master) reactor 56, catalyzer 57 in main reactor, first (master) stove 58, thermopair (not shown) in main reactor, glass cylinder 60, ice-cooled condenser 61, product liquid 62, inferior stove 63, secondary response device 64, catalyzer 65 in the secondary response device, the glass cylinder 66 and the ice-cooled condenser 67 that are used for secondary response device effluent, the product liquid 68 of secondary response device effluent, with gas chromatograph 67.

Two experiments are under atmospheric pressure carried out.The H-ZSM-5 that loads in first experiment use the first reactor and the GaZSM-5 (1-1) in the second reactor carry out.The second experiment uses the GaZSM-5 (1-1) that loads in two reactors of series connection to carry out.Temperature of reaction is set according to the performance of the catalyzer of filling, and the H-ZSM-5 that is used for the cracking rapeseed oil that wherein determines in experiment before and the optimal reaction temperature of GaZSM-5 (1-1) are respectively 400 ℃ and 350 ℃.Therefore, when containing H-ZSM-5, the first reactor (receive rapeseed oil as charging) is set under the temperature of reaction of 400 ℃, and when containing GaZSM-5, the first reactor is set under the temperature of reaction of 350 ℃.Early stage work (this early stage work shows that 450 ℃ is to be upward the optimum temps of BTEX with transformation of propane at GaZSM-5 (1-1)) based on the inventor, the second reactor that all contains GaZSM-5 (1-1) for two experiments is set in 450 ℃, to be converted from the steam product of the first reactor.In both cases, the first reactor contains the 10g catalyzer, and the second reactor contains the 5g catalyzer.Experiment SAP359 for H-ZSM-5 wherein afterwards be GaZSM-5 (, the experiment of the experiment that 1-1) (is respectively main reactor and secondary response device) number, and experiment SAP360 is for being the experiment of the experiment of GaZSM-5 (being respectively main reactor and secondary response device) number after GaZSM-5 wherein.

Before catalyzed conversion, GaZSM-5 (1-1) is heated to 500 ℃ in flowing nitrogen, then activates at least 1 hour under 500 ℃ under 30% hydrogen stream in nitrogen of 100mL/min.Reactivation process drives the Ga positively charged ion and enters in zeolite pore, and the Ga positively charged ion replaces the proton in zeolite.After activation step, with reactor cooling to required temperature of reaction.Co-fed nitrogen is set as 46.5ml/min, and the rapeseed oil flow set is 0.182ml/min.Reaction continues approximately 2 hours, charging 20g reactant within this time period.

Based on the difference of the grams of the product of the grams of reaction-ure feeding and collection, the total mass balance of carrying out each experiment.Product mainly comprises three parts: gas, liquid and coke.Table 8 provides reaction conditions and available from the product quality of the rapeseed oil cracking in each reactor, and the total mass balance.For these two experiments, mass balance is in 5wt%.Table 9 contains the composition as the product of summarizing of the weight percent calculating of total oily charging in table 8.

The oeverall quality balance that the rapeseed oil in two reactors of series connection of table 8. example II transforms

The product that the rapeseed oil available from two reactors of series connection of table 9. example II transforms or the productive rate of group

Hexane in the SAP284-287 (under 400 ℃ on H-ZSM-5 cracking rapeseed oil, referring to example I)+the 2.4wt% productive rate, the 9.81wt% hexane+productive rate of SAP359 gaseous product is high especially.This makes the inventor suspect BTEX product total condensation not when leaving the second reactor.Therefore, three gaseous product samples obtain in the SAP360 process with 30 minutes intervals, and use Agilent5975GC-MS to analyze to determine gas-phase product, hexane+cut of particularly reporting by miniature GC.Set up GC-MS only in order to determine the molecule greater than C3.Flame ionization detector shows 4 main peaks, and it is defined as benzene, toluene and dimethylbenzene by mass spectrum.There is some other molecule, can't determines them but concentration is lower.Therefore, the hexane in the gas of analyzing by miniature GC+can mainly be regarded as aromatic substance, and be contained in BTEX and gasoline-range productive rate summation.

As expected, in the future the steam product of autonomic response device is fed to the second reactor that is filled with GaZSM-5 and has increased overall organic liquid product (OLP) productive rate in the rapeseed oil cracking.As seen, the OLP output from the first reactor in the SAP359 experiment is 9.35g in table 8, and the second reactor of this experiment has increased the OLP of 0.29g.Also as seen in experiment SAP360, the catalyzer of filling gallium doping has further increased OLP in two reactors, as finding out by the 11.19gOLP in SAP360 relatively and the 9.64g OLP in SAP360.

Example II conclusion

Increase another reactor and can improve OLP productive rate and BTEX productive rate with the steam product that transforms available from the rapeseed oil cracking.Hexane+cut in gaseous product is uncondensable aromatic substance.When all (two) reactor charge have the catalyzer of gallium filling, obtain in this example the best overall yield of BTEX.Particularly, the cracking rapeseed oil produces 46.3%BTEX (suppose hexane+be uncondensable aromatic substance) on GaZSM-5 under 350 ℃, the second reactor that is filled with GaZSM-5 under increasing by 450 ℃ with total BTEX gain in yield to 51.22wt%.As in this example as mentioned above, by adding the second reactor that contains the GaZSM-5 catalyzer under 450 ℃, the BTEX gain in yield of the 39.45wt% that the cracking rapeseed oil obtains on H-ZSM-5 under 400 ℃ is to 43.82wt%.The inventor recognizes and can use further experiment to carry out the further improvement of aromatics yield.Possible parameters optimization be included in two in reactor beds gallium filling level, the catalytic amount in each, each temperature, with respect to material flow with respect to space velocity and other possible parameters of nitrogen feed.

The comparison of the algal oil cracking of example III on GaZSM-5 and HZSM-5

Algal oil (sample NL-72-32-03) stands under 400 ℃ (GaZSM-5,1.0Ga/ skeleton in zeolite-A1) and the catalytic cracking on the ZSM-5 (HZSM-5) of proton form at the ZSM-5 of gallium doping.The purpose of this operation is between these two kinds of catalyzer relatively to form from algal oil the formation of aromatic substance, particularly benzene, toluene, ethylbenzene and dimethylbenzene (BTEX), to be used for the fuel blend or as the raw material of chemical industry.Observe than HZSM-5, in the algal oil cracking process under same reaction temperature, GaZSM-5 produces more BTEX and paraffinic hydrocarbons still less (particularly propane).

Experiment uses the reactor assembly of 20g scale to carry out, and described reactor assembly has the single reactor of the 10g of being filled with catalyzer as above in example I.The result of these experiments shows, than the BTEX productive rate of the 38.9wt% during the cracking algal oil and the gasoline yield of 42.9wt% on HZSM-5 under the same conditions, cracking algal oil (NL-72-32-03) provides the BTEX productive rate of 46.8wt% and the gasoline yield of 48.3wt% on GaZSM-5.And than the 25.9wt% of HZSM-5, GaZSM-5 has reduced C ₁-C ₃Paraffinic hydrocarbons productive rate, thereby the C1-C3 paraffinic hydrocarbons of generation 16.7wt%.Than the 14.0wt% of HZSM-5, GaZSM-5 has also reduced propane yield, thereby produces the propane of 6.4wt%.

Experiment

The method of reporting according to example I prepares GaZSM-5, and described method originates in identical Zeolyst CBV5524G powder (50/1SiO2/A12O3), and described powder is converted into pill as example I, then load gallium in the mode identical with example I.Yet only gallium filling level used in this research is called " GaZSM-5 " in this example corresponding to 1.0Ga/ skeleton-Al in zeolite.Basic ZSM-5 material uses with its fully protonated form, and is called " HZSM-5 ".Due in work before, for the rapeseed oil raw material, HZSM-5 provides the highest BTEX productive rate under 400 ℃, and therefore, algal oil cracking experiment is also carried out at this temperature.The GaZSM-5 catalyzer activates at least 1 hour under 500 ℃ under 30% hydrogen stream in nitrogen of 100mL/min.The ion-exchange of Ga positively charged ion and proton in known this reactivation process acceleration zeolite.For HZSM-5, the same as usual, catalyzer is as the nitrogen flow that uses 46.5ml/min before cracking catalyst under 400 ℃ dry 2 hours.Suppose that algal oil density is 0.9g/mi, the 10g algal oil is corresponding to 11.1ml, and the algal oil flow is 0.185ml/min, corresponding to WHSV=1.0.Following the carrying out of cracking experiment:

● the 10g zeolite catalyst is filled in reactor

● reactor is packed in stove

● set up N ₂Stream

● for GaZSM-5, make reactor reach 500 ℃, catalyzer is activated

● temperature of reactor is set as 400 ℃

● the co-fed 0.0465SLM that is established as of nitrogen

● the charging of beginning algal oil, 0.185ml/min (corresponding to WHSV=1.0)

● reaction-ure feeding total amount, 11.1ml or 10g

The same as usual, based on the difference between the grams of the grams of reaction-ure feeding and the product of collection, carry out the total mass balance of at every turn testing.The product of collecting is divided into three parts: 1) gaseous product, it is by the continuously measured of miniature GC system, 2) product liquid of condensation, it is collected from the effluent of reactor in the trap of 0 ℃ of lower constant temperature, and 3) stay the coke on catalyzer.

Table 10 provides the oeverall quality balance available from the algal oil cracking on GaZSM-5 and HZSM-5.Can know and find out, than HZSM-5, GaZSM-5 produces more liquid and gas still less.The following discussion of detailed product analysis.

Product analysis

The reaction conditions of algal oil and mass balance in table 10. example III (reactant in each experiment is 10 grams)

In gas-phase product (referring to Fig. 7), along with gallium is added into catalyzer, C1-C3 paraffinic hydrocarbons productive rate reduces.For example, propane yield is reduced to 6.4wt% from 14.0wt%.Than the HZSM-5 of the hydrogen productive rate that 0.5wt% only is provided, GaZSM-5 provides the hydrogen productive rate of 2.0wt%.

Product liquid is also analyzed with quantitative BTEX content by GC-MS.Gasoline yield obtains via simulation distil.Than the HZSM-5 of the BTEX productive rate that produces 34.1wt%, GaZSM-5 produces the almost BTEX productive rate of 40.8wt% in product liquid.By simulation distil, GaZSM-5 provides the gasoline yield of 42.4wt% in liquid, and HZSM-5 provides 38.1wt%.By gallium being added into the HZSM-5 catalyzer, BTEX productive rate and gasoline yield have increased respectively 6.7wt% and 4.3wt% in liquid phase.Also shown for this bi-material, BTEX is the primary product in gasoline.Than 89.6% of HZSM-5, for GaZSM-5, the composition of BTEX is up to 96.4% in gasoline.

In experiment before, determined corresponding to hexane+real composition, it is by gas analysis instrument (miniature GC) report, and this substance classes proves almost pure benzene.This is justified, because the C in the product liquid of collecting ₆Cut is only almost benzene (as determining by GC-MS), and because works off one's feeling vent one's spleen with the liquid of collecting close to vapor liquid equilibrium.Therefore, if determined and be added into benzene productive rate in liquid phase from the hexane+productive rate of gas phase, can calculate the overall productive rate of two catalyzer.

Fig. 8 has shown the overall productive rate available from these two catalyzer.For the GaZSM-5 material, overall BTEX productive rate and gasoline-range products collection efficiency are respectively 46.8% and 48.3%, and the gasoline-range molecule 96.9% is BTEX.BTEX in product liquid (comprise hexane+) consists of 83.6%.These good productive rates can be compared with those productive rates (38.9% overall BTEX productive rate and 42.9% gasoline yield) of HZSM-5.For HZSM-5,90.7% of gasoline fraction is BTEX, and total product liquid (comprise hexane+) 78.2% be BTEX.Therefore, Fig. 8 has shown that total BTEX productive rate (" overall BTEX productive rate ") has increased by 7.9%, and gasoline yield has also increased by 5.4% by gallium is added into HZSM-5.

From example III, and the conclusion of the comparison of example I (rapeseed oil) and example III (algal oil)

For the algal oil cracking under 400 ℃, gallium is added into HZSM-5 has increased BTEX productive rate and gasoline yield.GaZSM-5 also produces significantly more hydrogen than HZSM-5, and this produces consistent with the aromatic substance that increases.

By checking example I (experiment SAP281) and example III (SAP383), can be relatively at preferred catalyst (GaZSM-5,1.0Ga/ skeleton in zeolite-A1) go up the cracking rapeseed oil than the result of algal oil.Single reactor and substantially the same operational condition and catalyzer are used in these two experiments, but example I SAP281 only processes rapeseed oil, and example III SAP383 only processes algal oil.Notice that SAP281 and SAP383 all carry out under the temperature of reactor of 400 ℃.Use the catalyzer cracking rapeseed oil of preferred gallium doping to produce the BTEX productive rate of 39.3wt-% and gasoline-range (60-225 ℃) productive rate of about 43wt-%.On the other hand, use the catalyzer cracking algal oil of preferred gallium doping to produce the BTEX productive rate of 46.8wt-% and the gasoline-range (60-225 ℃) of 48.3wt-%.Therefore, in identical or substantially the same process, be than rapeseed oil significantly, algal oil produces the BTEX of many 7.5wt% and the gasoline of much approximately 5wt-%.

EXAMPLE IV: the catalyzed conversion of fossil oil gas oil on Ga/ZSM-5 and HZSM-5

This example has been described the catalytic cracking at the gas oil (from Conoco Phillips) on the ZSM-5 (GaZSM-5) of HZSM-5 and Ga doping under 400 ℃, to compare with rapeseed oil and algal oil result from example I and III.The purpose of this operation is between these two kinds of catalyzer the relatively particularly formation of benzene, toluene and dimethylbenzene (BTEX) of aromatic substance, to be used for the fuel blend or as the raw material of chemical industry.Observe than the HZSM-5 gas oil cracking under same reaction temperature, Ga/ZSM-5 produces more BTEX and paraffinic hydrocarbons still less (particularly propane).Yet when being added into Ga in catalyzer, the increase of the BTEX productive rate of renewable oils (algal oil and rapeseed oil) is much bigger, and the overall gasoline yield of renewable oils is also larger.

Experiment

GaZSM-5 makes according to the method for reporting in example I, but in this example only gallium filling level used corresponding to 1.0Ga/ skeleton-A1 (Ga/ZSM-5) in zeolite.Basic ZSM-5 material uses (HZSM-5) with its fully protonated form.Due in example III for the algal oil raw material, H-ZSM-5 provides the highest BTEX productive rate under 400 ℃, so the gas oil cracking of this example experiment is also carried out at this temperature.The Ga/ZSM-5 catalyzer activates at least 1 hour under 500 ℃ under 30% hydrogen stream in nitrogen of 100mL/min.The ion-exchange of Ga positively charged ion and proton in known this activating process acceleration zeolite.For H-ZSM-5, the same as usual, catalyzer is as the nitrogen flow that uses 46.5ml/min before cracking catalyst under 400 ℃ dry 2 hours.The density calculation of gas oil is 0.88g/ml, makes 10g gas oil be equivalent to 11.4ml, and the gas oil flow is 0.189ml/min with corresponding to WHSV=1.0.

Gas oil cracking experiment can be summarized as follows:

A) the 10g zeolite catalyst is filled in reactor;

B) reactor is packed in stove;

C) set up N ₂Stream (46.5ml/min);

D) for Ga/ZSM-5, make reactor reach 500 ℃, catalyzer is activated;

E) 30% hydrogen stream 1hr in nitrogen;

F) then temperature of reactor is reduced to reaction conditions;

G) temperature of reactor is set as 400 ℃;

H) beginning gas-oil feed, 0.189ml/min (corresponding to WHSV=1.0); And

I) reaction-ure feeding total amount, 11.4ml.

Based on the difference between the grams of the product of the grams of reaction-ure feeding and collection, the total mass balance of carrying out each experiment.The product of collecting is divided into three parts: 1) gaseous product, it is by the continuously measured of miniature GC system, 2) product liquid of condensation, collect in the effluent of its reactor from trap and glass adapter under 0 ℃, and 3) coke, it is stayed on catalyzer, and simply records by of poor quality between live catalyst and the catalyzer that used.Table 11 provides the total mass balance available from the gas oil cracking on Ga/ZSM-5 and H-ZSM-5.Can know and find out, than H-ZSM-5, Ga/ZSM-5 produces more liquid and gas still less.The following discussion of detailed product analysis.

Mass balance and the reaction conditions of table 11. gas oil cracking experiment

Product analysis

Fig. 9 has shown the gas-phase product that produces in the gas oil cracking process.Be clear that, along with gallium doping zeolite, C1-C3 paraffinic hydrocarbons productive rate descends, and the amount of propane has reduced 2/3rds.Also be clear that, than the experiment of using H-ZSM-5, have the more hydrogen product of a large amount in the experiment of using Ga/ZSM-5.Use the hydrogen product of increase of zeolite of gallium doping with to relate to algal oil (example III) well relevant with the operation of rapeseed oil (example I) before cracking on Ga/ZSM-5, thereby the BTEX of demonstration increasing amount form by interpolation Ga.

In example before, corresponding to hexane+real composition be defined as almost pure benzene by miniature GC.This is considered to reasonably, because the C6 cut in the product liquid of collecting is only almost benzene (as determining by GC-MS), and because works off one's feeling vent one's spleen with the liquid of collecting close to vapor liquid equilibrium.Therefore, for this example, if will be added into from the hexane+productive rate of gas phase benzene productive rate in liquid phase, can calculate the overall productive rate of two catalyzer.

Product liquid is also analyzed by GC-MS, and with quantitative BTEX content, these results are included in following table 12.For comparison purposes, the result from the cracking (example III) of the cracking (example I) of rapeseed oil and algal oil also is included in table 12.For comparison purposes, except the result from the cracking (example III) of algal oil, draw in Figure 10 from the result of the cracking (this example) of gas oil.About gas oil feedstocks, than the 39.24wt% productive rate of H-ZSM-5, Ga/ZSM-5 produces the BTEX of 40.64% productive rate in product liquid.Than when the catalyzer that Ga is added into for rapeseed oil and algal oil raw material approximately 7% BTEX productive rate improve, Ga is added into H-ZSM-5 makes the BTEX productive rate from gas oil only increase 1.6wt%.Data also show, for this raw material, BTEX is the primary product in gasoline.

The productive rate of the benzene in wt% of the various raw materials of table 12. and catalyzer, toluene, ethylbenzene, dimethylbenzene, total BTEX and gasoline.All experiments are carried out under 400 ℃ and WHSV=1.0.

In Figure 11, the simulation distil of Conoco Phillips gas oil and the simulation distil of algal oil compare.The simulation distil of rapeseed oil is not shown in Figure 11, because rapeseed oil decomposed before evaporation.These raw material simulation distil curves can compare with the product simulation distil that provides in Figure 12.Gasoline yield from each product of gas oil, rapeseed oil and algal oil on H-ZSM-5 and GaZSM-5 catalyzer also obtains via simulation distil, and these results are included in last column of table 12.It may be noted that when raw material is gas oil, almost without impact, gasoline yield is approximately 48% in both cases on gasoline yield in the interpolation of Ga.Yet, for renewable oils, notice the remarkably influenced of the interpolation of Ga.

Figure 12 has also shown the difference from the product of various raw materials.Renewable oils produces the light product liquid of product liquid that produces than gas oil.In addition, due to algal oil and rapeseed oil raw material ratio gas oil heavier, therefore when renewable oils is raw material, the much bigger difference of the overall reduction of the boiling point distribution of generation raw material.

Conclusion from example IV

Can draw to draw a conclusion, in the gas oil cracking technique of this example, the interpolation of Ga has increased overall BTEX productive rate really slightly, but it has minimal effects to not having impact to overall gasoline yield.This forms contrast with the identical experiment (wherein when Ga is added into catalyzer, observing the large gain in yield of BTEX and gasoline) of using rapeseed oil (example I) and algal oil (example III).And, recently light from the product liquid of gas oil from the product liquid of renewable oils, thus draw the following conclusions: and renewable oils is easier to cracking generally.Therefore, can say the gallium modification for generation unpredictable consequence for the BTEX productive rate of the increase of renewable oils (comprising algal oil) and gasoline yield, and the gallium modification has minimal effects or do not have impact to BTEX and gasoline yield from gas oil.Can show on the minimal effects of gas oil or without impact, gallium cationic catalyst additive is provided to the FCC unit to prepare aromatic substance from algal oil or other renewable oils be effectively for increasing, simultaneously on any significance degree infringement from BTEX and the gasoline yield of gas oil.

Example V: the FCC cracking of algal oil

In part filling (gallium cationic catalyst) and part charging (algal oil) FCC operation, the major part of FCC catalyzer will remain conventional FCC cracking catalyst (as Y zeolite), and the major part of raw material will remain conventional FCC charging (as gas oil/vacuum gas oil).Therefore, interested is coke in conventional FCC condition and on using under conventional FCC catalyzer available from the yield structure of algal oil and catalyzer.This example has illustrated some embodiment of the fluid catalytic cracking of the algal oil of comparing with the fluid catalytic cracking of vacuum gas oil.For the other information of the structure and function of relevant conventional FCC unit, referring to example VIII and Figure 23.

According to method steps a-i as listed above the part that is entitled as " the selectable technology that obtains thick algal oil from biomass ", extract and give birth to Nannochloropsis oceanica (Nannochloropsis salina) acquisition algal oil from salt by HTT hydrothermal treatment consists and heptane solvent.Hydrothermal treatment step (the step b in method as listed above) was carried out under 260C 0.5 hour.Analyze referring to " the algal oil charging " as above shown in 4-6.

The algal oil charging is carried out catalytic cracking in miniature catalytic cracking (MAT) system.MAT equipment and test are at petroleum refining R﹠amp; Be known in D, and for many years it has designed relevant to extensive fluid catalytic cracking (FCC) cell height with developing.Consider that MAT test only needs several gram chargings, and commercial FCC unit can process the charging over 100mbpd, the predictive ability of MAT test is quite remarkable.As commercial FCC unit, the MAT test is at the about cracking temperature of 1000 °F and use extremely short catalyzer-charging duration of contact (1-5 second) to operate, and under atmospheric pressure use zeolite based catalysts.

In this example, MAT test be used for relatively algal oil charging (" thick algal oil ") FCC processing and from European refinery with reference to petroleum (especially, the vacuum gas oil of petroleum derivation (VGO), its contain about 10 quality % residual oil, have 22 API and the sulphur level of 0.61wt%) FCC processing.Following table 13 has shown the yield structure of the MAT test of standard VGO (data the first hurdle) and algal oil charging (data the second hurdle), and difference is calculated in the 3rd field and shown.

The FCC MAT test productive rate (wt%) of table 13. and the standard VGO charge ratio algal oil charging through extracting

Figure 13 has compared the algal oil charging and with reference to the transformation efficiency of oil VGO charging (be converted into overhead product and more the per-cent of the charging of light constituent (adding coke as gasoline)) in catalyst/oil ratio (C/O) scope.In this test, algal oil has the reactivity approximately identical with reference VGO; This can infer by noticing that the algal oil charging has approximately 50% the transformation efficiency suitable with VGO under identical C/O ratio.

Figure 14 shows that the coke yield of algal oil charging is significantly higher than the coke yield of VGO.This is important, because commercial-scale FCC unit operates as follows: when they had high coke yield, thermal equilibrium was urged to feedstock conversion more low-level.Therefore, due to its high coke yield, expect that the algal oil charging of this example demonstrates the transformation efficiency more much lower than VGO in commercial unit.

Productive rate from gasoline, LCO (overhead product scope material), DCO, TC2, TC3 and the TC4 of algal oil and VGO is shown in Figure 17-22.During the corresponding productive rate that should note the algal oil of the hydrotreatment of hanging oneself in following example VII also is shown in Figure 17-22, to be used for research in the impact of FCC first being processed hydrotreatment.

In the FCC unit, the heavier compound in the charging of unit (particularly 1000 °F+material) and basic nitrogenous compound are conducive to higher coke yield.Described basic nitrogenous compound with react as the acidic catalyst site in the zeolite of cracking catalyst and makes described acidic catalyst site poisoning, produce thus coke and reduction transformation efficiency.Oxygenatedchemicals also can help to increase coke yield, and helps separately lower transformation efficiency.

Therefore, in catalytic cracking process, the algal oil charging of this example demonstrates can be for the debatable coke yield in many FCC unit.This shows, therefore on the thermally equilibrated impact in unit, comprise that this will reduce the overall conversion (operating than " baseline " without the algal oil charging) of FCC unit without algal oil charging of hydrotreatment as remarkable combined feed total feed of per-cent due to coke in existing FCC unit.Therefore, some algal oil without hydrotreatment (for example, some is without the HTT hydrothermal treatment consists of hydrotreatment and the algal oil of solvent extraction) may be the problem relevant to coke on conventional FCC catalyzer.Some embodiment that this may affect the algal oil FCC operation of the gallium cationic catalyst of part filling and part charging for example causes than the lower overall conversion of baseline FCC operation.

Example VI: the hydrotreatment of algal oil and the FCC through the algal oil of hydrotreatment afterwards split Change

The hydrotreatment of the algal oil charging of example V (experiment 4SEBR, 5SEBR and 6SEBR) under various conditions carries out obtaining oily product.These experiments (Continuous Flow of H2, oil and catalyzer remain in well-stirred reactor under pressure and temperature simultaneously) in semibatch reactor are carried out.When the experiment of the every 1 hour residence time finished, oil was moved out of and analyzes as the product sample that is called " oily product ".See table in 14-16 than three analyses through the oily product of hydrotreatment of (table 4-6's) algal oil charging.

Table 14: cut quality %-algal oil charging and through the sample of hydrotreatment

(4SEBR-6SEBR)

Table 15.Compounds category-algal oil charging and through the summary of the sample of hydrotreatment

(4SEBR-6SEBR)

Table 16.Ultimate analysis-algal oil charging and through the sample of hydrotreatment

(4SEBR one 6SEBR)

Three variants of catalytic hydroprocessing use identical catalyzer under uniform temp (370 ℃), but carry out under the Three pressures of 1000psi to 1800psi.Especially, 4SEBR, 5SEBR and 6SEBR carry out under 1000psig, 1500psig and 1800psig pressure respectively.Hydrotreating catalyst is commercially available NiMo/A12O3, and it had carried out prevulcanized and processing before the semibatch reaction, make not reoxidize and can occur.Be used for the NiMo/A12O3 catalyzer of these hydrotreatments experiments for being used for processing the catalyst sample of Canadian oil-sand, it is believed that described Canadian oil-sand have the BET surface-area in the 150-250m2/g scope, micropore is in mean diameter scope and the pore structure of macropore in 1000-3000 dust scope of 50-200 dust.

Use is from the charging as the catalytic cracking in the above-mentioned MAT system in example V of the oily product of experiment 4SEBR, 5SEBR and 6SEBR.Operation is consistent than those operations of the comparison of VGO with the algal oil charging that is used for example V, thereby allows to compare the data from example V and this example.As mentioned above, the measurable commercial FCC performance of MAT test.Be created in the limited MAT data of the algal oil of hydrotreatment under 1500psig from the limited oily product sample of 5SEBR.

Table 17 has shown standard VGO (data the first hurdle) and through the yield structure of the MAT test of the oil of high severity hydrotreatment (6SEBR, data the second hurdle), difference is calculated in the 3rd field and shown.

The FCC MAT test of table 17. and the standard VGO charge ratio algal oil of processing through high-pressure hydrogenation

Figure 15 has shown algal oil charging and the VGO than example V, three kinds of algal oil reactivities in FCC technique through hydrotreatment.Than than the algal oil of hydrotreatment under low severity (4 and 5SEBR), algal oil (the 6SEBR of hydrotreatment under high severity more, 1800psig) demonstrate superior reactivity, higher through the oil ratio VGO of more high severity hydrotreatment reactivity.That is, under the identical C/O scope of about 2-2.5, the transformation efficiency through the algal oil of high severity hydrotreatment in the MAT test is higher than the transformation efficiency of VGO.Oil (5SEBR, 1500psig) through medium hydrotreatment is approximately identical with the reactivity of VGO, and very unexpectedly, the material that makes by hydrotreatment under 1000psi is lower than the reactivity of VGO and thick algal oil charging.

As shown in figure 16, with respect to those coke yields from the thick algal oil of example V, hydrotreatment has improved coke yield.Under the same conversion of about 70wt%, be similar to the coke yield of VGO from the coke yield of the algal oil of 1800-psig hydrotreatment.

During the productive rate of algal oil of hydrotreatment of hanging oneself in MAT test is included in Figure 17-22.Products collection efficiency is preferably under similar transformation efficiency and compares.Therefore, Figure 17-22 have shown the % by weight productive rate (y axle) of the key product of drawing with respect to the transformation efficiency (x axle) that obtains by change C/O.These crucial productive rates are discussed in following paragraph.

Figure 17 shows, than under similar transformation efficiency from those gasoline yields of VGO, from the algal oil charging of example V and lower through the gasoline yield of the counterpart (from the oily product of 4-6SEBR) of hydrotreatment.Figure 18 shows, than under similar transformation efficiency from those overhead product productive rates (LCO or " light cycle oil ") of VGO, from algal oil charging and higher through the overhead product productive rate of the counterpart of hydrotreatment.Figure 19 shows, than under similar transformation efficiency from the DCO of VGO, from algal oil charging (thick algal oil) and significantly lower through the DCO productive rate of the counterpart of hydrotreatment (" decanted oil " comes the heaviest and the most unworthy product of catalytic cracking).Figure 20-22 have shown the productive rate of the specific components lighter than gasoline (being TC2, TC3 and TC4).

Show by the yield structure that obtains through the MAT (FCC) of the algal oil (6SEBR) of high severity hydrotreatment test, even when considering the cost that high-pressure hydrogenation is processed, also can have the value higher than VGO through the algal oil of high severity hydrotreatment.Higher overhead product productive rate and the reduction of gasoline yield, and the remarkable minimizing of the DCO of low value has all increased the value through the algal oil of hydrotreatment.It should be noted that, the coke on the FCC catalyzer still less of the algal oil (6SEBR) of high severity hydrotreatment helps the thermal equilibrium in FCC, this then improved transformation efficiency and productive rate.

Therefore, in certain embodiments, before algal oil is improved, algal oil is carried out hydrotreatment in the FCC operation.According to some embodiment of aromatic substance disclosed herein and/or hydrogen preparation, this FCC operation is characterised in that part filling gallium cationic catalyst and part charging algal oil.Improved coke yield through the algal oil of hydrotreatment can affect optimum catalyst and algal oil per-cent with respect to transformation efficiency, but expects that above-mentioned gallium catalyzer and algal oil per-cent (for example 1-20wt% or 5-10wt%) are the reasonable starting points through the optimization of the algal oil FCC of hydrotreatment embodiment.

Therefore, some method of improvement algal oil can comprise:

A) obtain thick algal oil from algae bio matter, described thick algal oil for be included in (approximately 400-630 °F) in the overhead product boiling range and in the gas oil boiling range (approximately 630-1020 °F) and in the vacuum residue boiling range the full boiling range algal oil of the material of (approximately 1020 °F+), wherein overhead product adds that gas oil boiling range material adds up to 55wt% at least, and wherein some embodiment of this thick algal oil can be for example by the HTT hydrothermal treatment consists described before this paper and any number of acquisition the in solvent extraction process;

b) on one or more hydrotreating catalysts of the hydrotreatment that is suitable for fossil petroleum residual oil/pitch (comprising the oil/pitch from oil-sand or tar sand), and/or have the pore structure that comprises macropore and be characterised in that BET surface-area in the 150-250m2/g scope, on one or more hydrotreating catalysts of micropore in the mean diameter scope of 50-200 dust and the macropore in 1000-3000 dust scope, the thick algal oil of hydrotreatment, wherein said one or more hydrotreating catalysts can comprise Ni/Mo and/or Co/Mo on the aluminum oxide with described pore structure or silica-alumina carriers,

C) wherein hydroprocessing condition in following scope: 1000-2000psig (more generally 1500-2000psig), about 0.8-1.51/hr LHSV (more generally approximately 11/hr LHSV), 300-425 ℃ (more generally 350-400 ℃), typical gas/oil ratio rate is 2000scf/b at least;

D) by conventional separation vessel/method, separate the liquid oils through hydrotreatment from the hydrotreater effluent, usually mean the liquid oils of separating through hydrotreatment from hydrogen and gas; And

E) will be sent to machining cell through liquid oils or its cut of hydrotreatment, described machining cell is the FCC unit of catalyzer (for example at least some gallium cationic catalysts) of at least some gallium modifications that comprises any person of the gallium catalyzer embodiment that is selected from described in present disclosure.

Some selectable embodiment can comprise the step (b) of replacement, described step (b) is: the thick algal oil of hydrotreatment on one or more hydrotreating catalysts, described one or more hydrotreating catalysts are characterised in that the BET surface-area in about 150-250m2/g scope, and comprising the macropore of at least 1000 dusts, wherein said one or more hydrotreating catalysts can comprise Ni/Mo and/or Co/Mo on the aluminum oxide with described pore structure or silica-alumina carriers.Some selectable embodiment can comprise the step (b) of replacement, described step (b) is: the thick algal oil of hydrotreatment on one or more hydrotreating catalysts, described one or more hydrotreating catalysts are included at least about the macropore in 1000 dust scopes.Can for example comprise following one or more from the end product of the as above technique of this example: BTX factories, gasoline, kerosene, rocket engine fuel, diesel oil or lube basestock.Some method of this example can comprise as above method steps a-e, basically is comprised of as above method steps a-e or is comprised of as above method steps a-e.Algal oil/cut can be in as above step b and e few to whole scopes at the raw material that is used for machining cell, for example, be fed to the approximately 0.1 volume % of liquid starting material of described machining cell until 100 volume %.Yet, in many embodiment of as above step e, the oil through hydrotreatment derived from thick algal oil will be the small portion (for example 1-20wt% or 5-10wt%) of whole FCC raw material, and the gallium cationic catalyst will be the only part (for example 1-20wt% or 5-10wt%) of whole FCC catalyzer loading level.

Example VII: the thermal treatment of algal oil and the hydrotreatment through the algal oil of hydrotreatment afterwards With the FCC cracking

Before thick algal oil is fed to FCC operation described in example VI with some, but these thick algal oils of thermal treatment.Because the complexity of described some algal oil that extracts from biomass forms and/or high molecular weight material, the thermal treatment of first being processed can be effective for one or more in reducing following characteristic in catalytic unit arbitrarily: the coke on oxygen level and/or other content of heteroatoms, metal content, high molecular content, 1000 °F+content, 1020 °F+content, boiling range/distribution, viscosity and/or poisoning of catalyst and/or catalyst precursor.In certain embodiments, expect that several in these characteristics are relevant to catalyst deactivation, described catalyst deactivation is caused by poisoning (as the acidic site poisoning by basic nitrogen compound) in catalyst activity site and/or the coke that produces on catalyzer.In certain embodiments, thermal treatment will reduce the great majority or all in these characteristics.

Therefore, expection has alleviated available from the thermal treatment of whole thick algal oils of biomass catalyst deactivation and/or the generation of the coke on catalyzer that causes due to thick algal oil, extended thus catalyzer as the life-span in this unit of hydrotreater, or improved such as the thermal equilibrium in the continuous catalyst regeneration system rapidly of FCC unit.The heat treating method of this example can be combined with the hydrotreatment (referring to example VI) on macroporous catalyst, to improve catalyst life and/or the thermal equilibrium in downstream units.

Therefore, in this example, heat treating method can be applicable to some thick algal oil, and described method comprises:

A) obtain thick algal oil (for example by any person above-mentioned HTT technique) from algae bio matter, described thick algal oil for be included in (approximately 400-630 °F) in the overhead product boiling range and in the gas oil boiling range (approximately 630-1020 °F) and in the vacuum residue boiling range the full boiling range algal oil of the material of (approximately 1020 °F+), wherein overhead product adds that gas oil boiling range material adds up to 55wt% at least;

B) the thick algal oil of thermal treatment (all thick algal oil) in the following way: under the pressure in 0-1000psig (more generally 0-300psig) scope, under gas or thinner, thick algal oil is heated to the 300-450 ℃ of temperature in scope adding or do not add, and algal oil is remained on this temperature lower 0 minute to 8 hours, time of 0.25-8 hour or 0.5-2 hour more generally;

C) by conventional separation vessel/method, flow out thing from thermal treatment and separate through heat treated liquid oils, usually mean from hydrogen and gas and separate from coke/solid through heat treated liquid oils; And

d) on one or more hydrotreating catalysts of the hydrotreatment that is suitable for fossil petroleum residual oil/pitch (comprising the oil/pitch from oil-sand or tar sand), and/or have the pore structure that comprises macropore and be characterised in that BET surface-area in the 150-250m2/g scope, on one or more hydrotreating catalysts of micropore in the mean diameter scope of 50-200 dust and the macropore in 1000-3000 dust scope, thing is flowed out in hydrotreatment thermal treatment, wherein said one or more hydrotreating catalysts can comprise Ni/Mo and/or Co/Mo on the aluminum oxide with described pore structure or silica-alumina carriers,

E) wherein hydroprocessing condition in following scope: 1000-2000psig (more generally 1500-2000psig), about 0.8-1.51/hr LHSV (more generally approximately 11/hr LHSV), 300-425 ℃ (more generally 350-400 ℃), typical gas/oil ratio rate is 2000scf/b at least;

F) by conventional separation vessel/method, separate the liquid oils through hydrotreatment from the hydrotreater effluent, usually mean the liquid oils of separating through hydrotreatment from hydrogen and gas; And

G) will be sent to machining cell through liquid oils or its cut of hydrotreatment, described machining cell is the FCC unit of the catalyzer (for example at least some gallium cationic catalysts) that comprises at least some any number of gallium modifications of the gallium catalyzer embodiment that is selected from described in present disclosure.

Can for example comprise following one or more from the as above end product of technique: BTX factories, gasoline, kerosene, rocket engine fuel, diesel oil or lube basestock.Some method of this example can comprise as above method steps a-g, basically is comprised of as above method steps a-g or is comprised of as above method steps a-g.Algal oil/cut can be in as above step b, d and g few to whole scopes at the raw material that is used for machining cell, for example, be fed to the approximately 0.1 volume % of liquid starting material of described machining cell until 100 volume %.Yet, in many embodiment of as above step g, the oil through hydrotreatment derived from thick algal oil will be the only part (for example 1-20wt% or 5-10wt%) of whole FCC raw material, and the catalyzer of gallium modification will be the only part (for example 1-20wt% or 5-10wt%) of whole FCC catalyzer loading level.

In selectable embodiment, can revise the as above step of this example, make the only part (as last running) of thick algal oil be heat-treated, but combination through heat treated part (deducting formed any solid/coke in thermal treatment) and thick algal oil without heat treated part with for hydrotreatment and fluid catalytic cracking subsequently.

Example VIII: fluidized-bed process unit commercial applications

Some embodiment can comprise in the refinery unit that the renewable oils " spike " of a small amount of extremely operates on non-renewable raw material before relatively, and at least some gallium cationic catalysts are provided in the unit.For example, " relatively in a small amount " can mean 1-20wt% (more generally 5-10wt%) interpolation that renewable oils can be used as unit raw material, and the gallium cationic catalyst is as 1-20wt% (more generally 5-10wt%) interpolation of unit catalyzer.This " spike " method may be effective especially in fluidized catalyst technique unit (for example FCC unit), as described further below.

As schematically showing in Figure 23, with conventional FCC heating raw materials and be sprayed to the base portion of standpipe (vertical or acclivitous pipeline), at the base portion place of standpipe through the raw material contact of the preheating fluidized zeolite catalyst under approximately 950 to 1030 °F (about 510 to 555 ℃) usually.The catalyzer of heat makes raw materials evaporate and catalytic cracking reaction, and described cracking reaction is decomposed into lighter component with high-molecular-weight hydrocarbons, comprises LPG (liquefied petroleum gas is as C3-C4 alkene) and acyclic or cyclic hydrocarbon (C5-C12).Catalyzer-hydrocarbon mixture upwards flows through standpipe several seconds (for example 2-4 second) only, and then mixture separates via cyclonic separator.The hydrocarbon of catalyst-free is sent to fractional column to separate shorter hydrocarbon product (for example C3-C12 hydrocarbon) from heavier fuel.The heavier fuel volatility of shorter hydrocarbon (the many gasoline product that are suitable as in shorter hydrocarbon) is stronger.Heavier fuel comprises under atmospheric pressure diesel oil and the rocket engine fuel of fractionation between about 200 ℃ to 350 ℃.

In the process of upwards advancing in standpipe, cracking catalyst is reacted " consumption ", described reaction deposit coke on catalyzer, and greatly reduce activity and selectivity.The process that coke forms is important for overall process, because its H/C with gaseous product (hydrogen/carbon) ratio increases to the scope that more is applicable to gasoline.The catalyzer that consumes is from breaking away from through the hydrocarbon steam of cracking and be sent to stripper, and it contacts to remove the hydrocarbon in remaining in catalyst pores with steam at the stripper place.Then, the catalyst stream of consumption enters in fluid bed regenerator, uses air (or air adds oxygen in some cases) that coke is burnouted at described fluid bed regenerator place, recovering catalyst activity, and provides essential heat for next reaction cycle.Then, mobile to riser base through the catalyzer of regeneration, thus repeat described circulation.

Usually catalyzer and additive are added into the FCC unit, described FCC uses the system that comprises separately hopper and lock hopper in the unit.Minimum catalyzer add speed when being trapped in revivifier stack gas when the fines that leaves and going to the oil of main fractionator from standpipe/reactor in cyclone system physical abrasion and the loss of FCC catalyzer determine.Therefore, the catalyzer fines is occurring in the slurry oil also referred to as decanted oil or DCO sometimes.Depend on productive rate required in activity of conversion and FCC, catalyzer/additive is added into FCC with the speed higher than this Physical Loss or Damage.For example, if need the more high reactivity of catalyzer/additive, add live catalyst/additive with higher speed.Therefore the Physical Loss or Damage that surpasses catalyzer/additive due to this speed needs to remove some catalyzer (" tank farm stock (inventory) " of equilibrium catalyst/additive) in the unit to keep the tank farm stock of catalyzer/additive constant.The tank farm stock of the catalyzer in the unit is commonly referred to " balance " catalyzer/additive, because it comprises different steps and the active catalyzer/additive that causes in the unit owing to being added in time.As adding, make charge tank and lock hopper system carry out the removal of this tank farm stock (equilibrium catalyst/additive), described hopper and lock hopper system can will be transported to ultimate disposal from the catalyzer/additive of revivifier is pneumatic.FCC catalyzer and additive system are all based on identical principle, but they are the mechanical separation system, so the interpolation speed of FCC catalyzer and additive can change to optimize them independently, and therefore optimize whole system.

When renewable oils and gallium cationic catalyst are in 1-20wt% or 5-10wt% scope (as institute's discussion before this paper), expect that the change (preparing aromatic substance from renewable oils to comprise according to of the present invention) to this conventional FCC cracking technique is minimum.Conventional FCC cracking catalyst keeps as the main ingredient of the catalyzer that comprises in the unit, for example is the 80-99wt% of catalyzer or 90-95wt% (when the gallium cationic catalyst provides with 1-20wt% or 5-10wt% respectively).The gallium cationic catalyst with as requiredly add or remove by above-mentioned additive hopper and lock hopper system.Yet, can carry out some changes to for example duration of contact, temperature and/or catalyst/oil ratio.Although in view of the gallium cationic catalyst in example shows its optimum performance and wishes to reduce the FCC contact temperature of catalyst under about 400 ℃, but in view of 510-555 ℃ of the most of FCC operational requirement on gas oil and/or heavy gas oil, it can not accomplish this point.

Example IX: the technique unit commercial applications of specific construction

In certain embodiments, refinery unit can specific construction be used for only processing renewable oils to produce the productive rate of good BTEX and/or gasoline and hydrogen on catalyzer, and described catalyzer is only the gallium cationic catalyst or is essentially the gallium cationic catalyst.A kind of unit of specific construction like this can be similar to UOP Cyclar ^TMThe unit, it comprises moving-bed and the coke burning regeneration section of described gallium cationic catalyst, as schematically drawing in Figure 24.Perhaps, for example, the fixed-bed reactor unit of specific construction can be effectively.Regeneration in two kinds of unit can be defined as only coke burning, reduce in the routine operation process in reactor subsequently.

As understood by the skilled person, can optimize two unit about temperature, pressure, flow, gallium loading level etc.In some embodiment of fill pattern under WHSV=1.0 structure, reactor will 350-450 ℃, more preferably in approximately operation under 400 ℃.Other contact structures and condition can produce the optimization temperature of 450-500 ℃, particularly when WHSV＞1.0.The unit of these specific construction use as 80-100wt% or more preferably the gallium positively charged ion of 90-100wt% keep the catalyzer of catalyzer, preferably in 80-100wt%, the more preferably upper operation of the renewable oils of 90-100wt% (for example algal oil).About conventional UOP Cyclar ^TMThe information of unit can be available from Uop Inc. (UOP, Des Plaines, Illinois, U.S.A.) of Illinois, USA moral Si Pulansi.Can be available from several petroleum refining unit design company about the information of fixed-bed reactor unit.

Can notice by as above describing (comprising example I-IX) in detail, many embodiment can be described as the method for the preparation of BTEX or gasoline, described method comprises: the catalyzer of the raw material that comprises at least a renewable oils and the gallium that comprises the catalytic activity form is contacted, comprise the product stream of BTEX with preparation.Described renewable oils can be for example rapeseed oil, algal oil, from the algal oil of green alga or blue-green algae extraction, or other renewable oils or its cut.It may be noted that at renewable oils to be that in some embodiment of technique of rapeseed oil, BTEX can be present in the productive rate greater than 35wt-% in described product stream by the data of this paper.It may be noted that at renewable oils to be that in some embodiment of technique of algal oil, BTEX can be present in the productive rate greater than 42wt-% in described product stream by the data of this paper.In in these embodiments some, described product stream comprises the productive rate greater than 15%wt-% benzene.Described catalyzer can be the zeolite catalyst of gallium modification, thereby for example comprises the gallium positively charged ion with the about ratio of 1/1Ga/ skeleton-Al.Described contact can be carried out in many reactor/vessel/standpipes, for example: at single reactor, series reaction device, a series of at least the first reactor and the second reactor (wherein remove the intermediate product stream of liquid between first and second reactor, and from the steam feed of the first reactor to described the second reactor), fixed-bed reactor, in the standpipe of moving catalyst bed and/or fluid catalytic cracking unit.In some embodiment that contacts in standpipe, contact can for example be carried out at 510 to 555 ℃ of temperature or at 400-555 ℃ of temperature.Described contact can be carried out 2-4 second.In certain embodiments, described renewable oils be extract from algae with described the contact between undressed algal oil.In certain embodiments, described algal oil is processed in RBD technique and/or degumming technology, but in certain embodiments, algal oil is not processed in RBD technique and/or degumming technology.In certain embodiments, before described contact, the hydrotreatment of described algal oil.In certain embodiments, catalyzer can be one or more zeolites of the gallium doped forms in the aperture that has 10 Sauerstoffatoms in the aperture-alumina base body catalyst, and for example it is selected from: ZSM-5, ZSM-11, ZSM-23, MCM-70, SSZ-44, SSZ-58, SSZ-35 and ZSM-22.Some embodiment can be described as: a kind of method for prepare aromatic substance (for example for the BTEX raw material or for gasoline) and/or hydrogen from renewable oils, described method comprises: the reactor vessel or the standpipe that contain catalyzer are provided, and described catalyzer comprises the gallium cationic catalyst; And raw material is contacted with described catalyzer; Wherein said raw material comprises and is selected from following renewable oils: derived from the oil of the biomass of survival in 50 years in the past; Rapeseed oil; Extract from the oil that comprises the vegetables of corn, soybean, sunflower and jowar; Algal oil from naturally occurring algae; Algal oil from the algae of gene modification; Oil from seed; Oil from fungi; And from the oil of light compositing or non-photosynthetic bacterium.Described renewable oils can be the percentage of whole chargings of these the whole bag of tricks, for example at the approximately 1wt% of described raw material (or even still less, for example 0.01wt%) until in the 100wt% scope.For example, described renewable oils can be 1-20wt%, 50-100wt%, the 80-100wt% of described raw material, or the 90-100wt% of whole raw materials.In certain embodiments, the catalyzer that comprises the gallium of above-mentioned catalytic activity form and/or gallium cationic catalyst can account for any per-cent of whole catalyzer of described method, for example the 1wt% of described raw material (or even still less, for example 0.01wt%) is until 100wt%.For example, the catalyzer that comprises the gallium of catalytic activity form and/or gallium cationic catalyst can be 1-20wt%, 50-100wt%, 80-100wt% or the 90-100wt% of described raw material.In certain embodiments, the weight percent that comprises the catalyzer of the gallium of catalytic activity form and/or gallium cationic catalyst in reactor vessel or standpipe equals renewable Weight ratio of oil in the method raw material.In certain embodiments, described standpipe is fluid catalytic cracking unit (FCC) standpipe, and catalyzer also comprises Y-zeolite FCC catalyzer in described standpipe, makes FCC operate on the catalyzer/additive of the catalyzer that comprises the gallium that comprises the catalytic activity form and/or gallium cationic catalyst, Y-zeolite and optional other conventional FCC additives.In certain embodiments, described reactor vessel is the moving-bed container, and it is adapted to make described catalyzer to move through reactor vessel by gravity.In certain embodiments, the temperature that contacts with catalyzer is the high temperature in 375-425 ℃ or 350-555 ℃ of scope, but in other embodiments, based on the requirement of the catalyzer of gallium catalyst mix, described temperature can be different from these scopes.In certain embodiments, interested especially is renewable oils available from non-dimension pipe photosynthetic organism body, for example naturally occurring algae or cyanobacteria, or the algae of gene modification or cyanobacteria.In certain embodiments, renewable oils be selected from other following components and mix or make up: one or more petroleum fractionss, one or more refining petroleum products or cut, naphtha, gasoline, rocket engine fuel, diesel oil and their arbitrary combination.Some embodiment of the present invention can comprise any renewable oils product that the modification method by any person who comprises aforesaid method makes, and for example is used for the stream that is rich in BTEX of petrochemical plant or other purposes, or gasoline and/or other fuel.

In this manual, temperature range, hold-time/residence time/LHSV, gas/oil ratio rate, in the BET surface of m2/g, in the aperture of dust, provide in many embodiment of the present invention in the pressure of psig and/or other scopes of variable.Should be appreciated that, described scope is intended to comprise all sub-ranges, and be intended to be included in temperature in each broad range of providing, hold-time/residence time/LHSV, gas/oil ratio rate, in the BET surface of m2/g, in the aperture of dust, in each increasing amount of pressure and its dependent variable of psig.For example, although mention the broad range of the pressure of 1000-2000psig, some embodiment can comprise any person or any pressure in any person in following sub-range in following sub-range: 1000-1050,1050-1100,1100-1150,1150-1200,1200-1250,1250-1300,1300-1350,1350-1400,1400-1450,1450-1500,1500-1550,1550-1600,1600-1650,1650-1700,1700-1750,1750-1800,1800-1850,1850-1900,1900-1950 and 1950-2000psig.For example, although mention the broad range of 300-425,300-450 and 350-555 ℃, some embodiment can for example be included in the arbitrary temp in any person of these scopes, or any 10 ℃ of sub-ranges.The example in 10 ℃ of sub-ranges of the scope of 300-450 ℃ is: 300-310,310-320,320-330,330-340,340-350,350-360,360-370,370-380,380-390,390-400,400-410,410-420,420-430,430-440,440-450 ℃.The example in 10 ℃ of sub-ranges of the scope of 350-555 ℃ is: 350-360,360-370,370-380,380-390,390-400,400-410,410-420,420-430,430-440,440-450,450-460,460-470,470-480,480-490,490-500,500-510,510-520,520-530,530-540,540-550 and 545-555 ℃.

Present disclosure also comprises those values of (wherein write or show in table or figure such as the value of degree, mass percent or weight percent) insertion " approximately " before each value, and it may be suitable in some embodiment of present disclosure that those of ordinary skills will understand " approximately " these values.

Although shown and described some embodiment at this paper, it will be apparent to one skilled in the art that this embodiment only provides by way of example.Do not departing under present disclosure, those skilled in the art will expect many modification, change and replacement.The various alternative that should be appreciated that the embodiment of the specific description of this paper can be used for implementing the present invention, and the present invention extends to all equivalents in following claims scope.

Claims (54)

1. method for the preparation of BTEX or gasoline, described method comprises:

The catalyzer of the raw material that comprises at least a renewable oils and the gallium that comprises the catalytic activity form is contacted, comprise the product stream of BTEX with preparation.

2. method according to claim 1, wherein said renewable oils is rapeseed oil.

3. method according to claim 2, wherein BTEX is present in described product stream with the productive rate greater than 35wt-%.

4. method according to claim 1, wherein said renewable oils is algal oil.

5. method according to claim 4, wherein said renewable oils are the thick algal oil that extracts from green alga or blue-green algae.

6. method according to claim 4, wherein BTEX is present in described product stream with the productive rate greater than 42wt-%.

7. method according to claim 3, wherein said product stream comprises the productive rate greater than the benzene of 15wt-%.

8. method according to claim 6, wherein said product stream comprises the productive rate greater than the white benzene of 15wt-%.

9. the described method of any one according to claim 1-8, wherein said catalyzer is zeolite catalyst, described zeolite catalyst through the gallium modification to comprise the approximately gallium positively charged ion of 1/1Ga/ skeleton-Al ratio.

10. the described method of any one according to claim 1-8, wherein said contact is carried out in single reactor.

11. the described method of any one according to claim 1-8, wherein said contact is carried out at least in a series of the first reactor and the second reactor, wherein remove the intermediate product stream of liquid between described the first reactor and the second reactor, and will be from the steam feed of described the first reactor to described the second reactor.

12. the described method of any one according to claim 1-8, wherein said contact is carried out in fixed-bed reactor.

13. the described method of any one according to claim 1-8, wherein said contact is carried out in moving catalyst bed.

14. the described method of any one according to claim 1-8, wherein said contact is carried out in the standpipe of fluid catalytic cracking unit.

15. method according to claim 14, wherein said contact is carried out at 510 to 555 ℃ of temperature.

16. method according to claim 14, wherein said contact is carried out at 400-555 ℃ of temperature.

17. method according to claim 14, wherein said contact are carried out 2-4 second.

18. according to claim 1, the described method of any one in 4-6 and 8, wherein said renewable oils be extract from algae with described the contact between crude algal oil.

19. according to claim 1, the described method of any one in 4-6 and 8, wherein said algal oil is processed in RBD technique and/or degumming technology.

20. according to claim 1, the described method of any one in 4-6 and 8, wherein said algal oil is not processed in RBD technique and/or degumming technology.

21. wherein said algal oil hydrogen treatment before described contact according to claim 1, the described method of any one in 4-6 and 8.

22. the described method of any one according to claim 1-21, wherein said renewable oils is the 1-100wt% of described raw material.

23. the described method of any one according to claim 1-21, wherein said renewable oils is the 1-20wt% of described raw material.

24. the described method of any one according to claim 1-21, wherein said renewable oils is the 80-100wt% of described raw material.

25. the described method of any one according to claim 1-21, wherein said renewable oils is the 90-100wt% of described raw material.

26. the described method of any one according to claim 1-21, wherein said catalyzer is one or more zeolites-alumina base body catalyst of the gallium doped forms in the aperture that has 10 Sauerstoffatoms in the aperture.

27. method according to claim 26, wherein said catalyzer are the zeolite catalyst that is selected from following gallium doped forms: ZSM-5, ZSM-11, ZSM-23, MCM-70, SSZ-44, SSZ-58, SSZ-35 and ZSM-22.

28. a method that is used for preparing from renewable oils BTEX aromatic substance and/or hydrogen, described method comprises:

The reactor vessel or the standpipe that contain catalyzer are provided, and described catalyzer comprises the gallium cationic catalyst; And

Raw material is contacted with described catalyzer;

Wherein said raw material comprises and is selected from following renewable oils: derived from the oil of the biomass of survival in 50 years in the past; Rapeseed oil; Extract from the oil that comprises the vegetables of corn, soybean, sunflower and jowar; Algal oil from naturally occurring algae; Algal oil from the algae of gene modification; Oil from seed; Oil from fungi; And from the oil of light compositing or non-photosynthetic bacterium.

29. method according to claim 28, wherein said renewable oils are the 1-100wt% of described raw material, and the described gallium cationic catalyst 1-100wt% that is the described catalyzer in described reactor vessel or standpipe.

30. method according to claim 28, wherein said renewable oils are the 1-20wt% of described raw material, and the described gallium cationic catalyst 1-20wt% that is the described catalyzer in described reactor vessel or standpipe.

31. method according to claim 28, wherein said renewable oils are the 80-100wt% of described raw material, and the described gallium cationic catalyst 80-100wt% that is the described catalyzer in described reactor vessel or standpipe.

32. method according to claim 28, wherein said renewable oils are the 90-100wt% of described raw material, and the described gallium cationic catalyst 90-100wt% that is the described catalyzer in described reactor vessel or standpipe.

33. method according to claim 28, wherein the described weight percent of gallium cationic catalyst equals renewable Weight ratio of oil in described raw material in described reactor vessel or standpipe.

34. the described method of any one according to claim 28-33, wherein said standpipe are fluid catalytic cracking unit (FCC) standpipe.

35. method according to claim 34, wherein said catalyzer also are included in the Y-zeolite FCC catalyzer in described standpipe.

36. the described method of any one according to claim 28-33, wherein said reactor vessel is the moving-bed container, and described moving-bed container is adjusted into and makes described catalyzer move through described reactor vessel by gravity.

37. the described method of any one according to claim 28-33, wherein said reactor vessel is fixed-bed reactor.

38. the described method of any one according to claim 28-33, wherein said high temperature is in the scope of 375-425 ℃.

39. the described method of any one according to claim 28-33, wherein said high temperature is in the scope of 350-555 ℃.

40. a method that is used for preparing from the renewable oils available from non-dimension pipe photosynthetic organism body BTEX aromatic substance or gasoline, described method comprise, the catalyzer of the raw material that comprises described renewable oils and the gallium that keeps the catalytic activity form is contacted.

41. described method according to claim 40, wherein said catalyzer is one or more zeolites of the gallium doped forms in the aperture that has 10 Sauerstoffatoms in the aperture-alumina base body catalyst.

42. described method according to claim 40, wherein said catalyzer is the zeolite catalyst that is selected from following gallium doped forms: ZSM-5, ZSM-11, ZSM-23, MCM-70, SSZ-44, SSZ-58, SSZ-35 and ZSM-22.

43. described method according to claim 40, wherein said catalyzer comprises the gallium positively charged ion.

44. described method according to claim 40, wherein said high temperature is in the scope of 350-555 ℃.

45. described method according to claim 40, wherein said high temperature is in the scope of 375-425 ℃.

46. described method according to claim 40, wherein said raw material is 100% the oil available from non-dimension pipe photosynthetic organism body.

47. described method according to claim 40, wherein said raw material is the oil available from non-dimension pipe photosynthetic organism body of 90-100%.

48. described method according to claim 40, wherein said raw material is the oil available from non-dimension pipe photosynthetic organism body of 80-100%.

49. described method according to claim 40, wherein said raw material is the oil available from non-dimension pipe photosynthetic organism body of 50-100%.

50. described method according to claim 39, wherein said raw material is the oil available from non-dimension pipe photosynthetic organism body of 1-20%.

51. the described method of any one according to claim 46-50, wherein said oil available from non-dimension pipe photosynthetic organism body extracts from naturally occurring algae or cyanobacteria.

52. the described method of any one according to claim 46-50, wherein said oil available from non-dimension pipe photosynthetic organism body extracts algae or the cyanobacteria from the gene modification.

53. the described method of any one according to claim 47-52 is not wherein as being that remainder available from the raw material of the oil of non-dimension pipe photosynthetic organism body is selected from as follows: one or more petroleum fractionss, one or more refining petroleum products or cut, naphtha, gasoline, rocket engine fuel, diesel oil and their arbitrary combination.

54. renewable oils product that makes by any number of method that comprises according to claim 1-53 described methods.

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