CN102417829B - Catalytic conversion method capable of reducing benzene content of gasoline - Google Patents
Catalytic conversion method capable of reducing benzene content of gasoline Download PDFInfo
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- CN102417829B CN102417829B CN201110064391.XA CN201110064391A CN102417829B CN 102417829 B CN102417829 B CN 102417829B CN 201110064391 A CN201110064391 A CN 201110064391A CN 102417829 B CN102417829 B CN 102417829B
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Abstract
The invention provides a catalytic conversion method capable of reducing the benzene content of gasoline. The method is as follows: the benzene-containing gasoline and alcohol contact with a catalytic cracking catalyst in a plurality of reaction zones in turn and gasoline with low benzene is separated from the reacted mixture, wherein the reaction zones comprise a first reaction zone and other reaction zones following the first reaction zone, the contact temperature of any reaction zone following the first reaction zone is lower than the temperature of the previous adjacent reaction zone, and the residence time of the reaction zone is longer than that of the previous adjacent reaction zone. By adopting the method provided by the invention to treat the benzene-containing gasoline, the benzene content of the gasoline can be reduced by above 65vol.%; as the alcohol reacts with benzene and is converted to gasoline fractions, thus the yield of gasoline can be increased; and as benzene reacts with the alcohol to be converted into arene, the gasoline octane number can be improved.
Description
Technical field
The invention relates to a kind of catalysis conversion method that reduces Determination of Benzene In Gasoline.
Background technology
As the important component part of the tail gas pollution of motor-driven vehicle comprehensive regulation, reduce content of sulfur in gasoline, improve Aromatic Hydrocarbon in Gasoline and olefin(e) centent, improving constantly quality of gasoline has been the instant task that petroleum chemical industry faces, especially the benzene in gasoline is a kind of carcinogenic substance, in gasoline, can cause severe contamination to atmosphere by evaporation and incomplete combustion, there is strict restriction countries in the world to Determination of Benzene In Gasoline.The Europe IV standard that implement in the EUROIII Emission Standard, 2005 implemented for 2000 in world fuel standards II class specification index and Europe is limited to 1.0 volume % in the requirement of benzene content in to motor spirit.EPA is in atmosphere Toxic rules (MAST) subordinate phase of motor vehicle emission, and further proposition will be reduced to 0.62 volume % by average benzene content in the gasoline of the whole America in 2011.China will implement in full the quality index (GB17930-2006) of motor spirit state III before 31 days December in 2009, required Aromatic Hydrocarbon in Gasoline content to be not more than 40% (volume), and benzene content is not more than 1.0 volume %.In domestic gasoline product, catalytically cracked gasoline ratio is about 80 % by weight, and in catalytically cracked gasoline, benzene content is approximately 0.5%-1.3 volume %.Therefore, reduce Determination of Benzene In Gasoline and just become petroleum chemical industry urgent problem.
Reduce Determination of Benzene In Gasoline and have following several method: saturated, isomerization, benzene extracting, absorption method and alkylation.First two method all needs to consume hydrogen, and owing to containing a large amount of alkene in catalytically cracked gasoline, thereby hydrogenation de-benzene process is not suitable for catalytically cracked gasoline; Benzene In Gasoline removes common employing Aromatic Extraction Process, and benzene content is lower in catalytically cracked gasoline, adopt Aromatic Extraction Process, cause operation easier and running cost to increase considerably, from economic angle, it is unaccommodated adopting Aromatic Extraction Process to reduce FCC benzene content in gasoline; Absorption method is to utilize specific sorbent material selective adsorption Benzene In Gasoline, the method shortcoming is loss yield of gasoline and high-octane number component, because the loading capacity of sorbent material is limited, benzene and other polar compound have a strong impact on adsorption efficiency as the competitive adsorption of alkene, other aromatic hydrocarbons; Unique conversion benzene and do not consume hydrogen, the technique of not losing octane value is benzene alkylation technology.
US4827069 discloses a kind of technique that reduces Determination of Benzene In Gasoline, heavy petrol or catalytically cracked gasoline are carried out cut cutting by this technique, and its rich benzene cut is mixed with the olefin feedstock such as ethene, propylene, under the effect of solid acid catalyst, there is the alkylated reaction of alkene and benzene.This process using dense fluidized bed bioreactor, catalyzer is the shape-selective catalyst based on ZSM-5 family, Benzene In Gasoline reacts with light olefin and forms high-octane alkyl mononuclear aromatics.On this basis, US4975179 further discloses and has utilized the middle above alkene of C5 of gasoline fraction (petroleum naphtha) and benzene that alkylating technique occurs, and the benzene in FCC gasoline can be converted into high-octane alkylbenzene, and still stay in gasoline.Like this, can play and reduce benzene content in gasoline and increase the object of gasoline octane rating, and total aromaticity content in gasoline changes little.
CN101372441A discloses a kind of employing fixed bed or fluidized-bed, the method of utilizing ethene and Benzene In Gasoline and alkylation catalyst contact reacts to generate ethylbenzene reduces Determination of Benzene In Gasoline, alkylation catalyst is ZSM-5/ZSM-11 cocrystallization Si-Al zeolite, be characterized in that low-concentration ethane does not need to purify, contain the gasoline containing benzene of benzene without dehydration, Benzene In Gasoline transformation efficiency is greater than 45%.
WO9853029 discloses a kind of method that simultaneously reduces Benzene In Gasoline and sulphur content.Sour gasoline with the cut that is rich in benzene through two step process processes, first being gasoline reacts selecting on shape an acidic catalyst with the cut that is rich in benzene, in this process, gasoline olefin and benzene and other aromatic hydrocarbons generation alkylated reaction generate alkylaromatic hydrocarbon, and the reactant of generation is converted into H through hydrotreatment by the sulfocompound in gasoline
2s.The method not only can reduce content of sulfur in gasoline, and can reduce benzene content in gasoline, and benzene content in gasoline declines approximately 20%.
CN1219026C disclose a kind of distillate or lighting end with reformed gasoline by weight 1: 1-3: 1 mixes, on ultrafine particle zeolite alkylated catalyst, carry out the method for alkylated reaction reduction Determination of Benzene In Gasoline.This ultrafine particle zeolite aromatized catalyst total acid content is low, and especially L acid is lower, and duct is more unimpeded, and in the clean gasoline of production, alkene and benzene content are low.
US5491270 discloses a kind of method that is rich in benzoline benzene and macromole olefin alkylation, the method will contain the gasoline of benzene and contain compared with the gasoline of macromole (being greater than C5) alkene and contain ZSM-5 molecular sieve catalyzer contact reacts, or is rich in benzene, alkene (being greater than C5) simultaneously and contains ZSM-5 molecular sieve catalyzer contact reacts.The feature of this process is to be rich in benzoline and C5 alkene carries out alkylation, and the product obtaining is mainly C10 alkylaromatic hydrocarbon.In this process, benzene content at least reduces by 25 % by weight, and C5 olefin(e) centent has reduced by 60 % by weight.
US5120890 discloses a kind of petroleum naphtha containing benzene and/or toluene and alkylating reagent to carry out liquid-phase alkylation and reaches and reduce benzene content and put forward high-octane process.Alkylating reagent can with in the form injecting reactor of multistage with the transformation efficiency of avoiding side reaction and reach benzene more than 70%.Alkylating reagent comprises ethene, propylene, butylene, methyl alcohol and ethanol.Catalyzer is solid phosphoric acid catalyst.
Can reduce benzene content although adopt alkylation to fall benzene technological line, but often need to introduce the low-carbon alkene such as ethene, propylene of high value, subsequent separation process complexity, facility investment increases, and when the above alkene generation of benzene and C5 alkylated reaction, be easy to generate the above cut of C12, reduced gasoline yield.Therefore,, in order to meet the gasoline quality standard of increasingly stringent, be necessary to develop and a kind ofly significantly reduce Determination of Benzene In Gasoline and don't affect quality of gasoline and the method for yield.
Summary of the invention
The object of the invention is to provide on the basis of existing technology a kind of catalysis conversion method that reduces benzene content in gasoline.
The catalysis conversion method of reduction benzene content in gasoline provided by the invention comprises and will contact in multiple reaction zones successively with catalytic cracking catalyst with alcohol containing the gasoline of benzene, isolates the gasoline of benzene content reduction from reacted mixture; Described multiple reaction zone comprises the later reaction zone in the first reaction zone and the first reaction zone, the Contact Temperature of later any one reaction zone, the first reaction zone is lower than the temperature of adjacent previous reaction zone, and the residence time of this reaction zone is longer than the residence time of adjacent previous reaction zone.
The catalysis conversion method of reduction benzene content in gasoline provided by the invention, by mix a certain amount of alcohol in gasoline, utilizes the alkylated reaction of alcohol and benzene to reduce Determination of Benzene In Gasoline, improves quality of gasoline simultaneously; By by containing benzoline and catalytic cracking catalyst successively by multiple reaction zones that temperature reduces gradually, the residence time extends gradually, further reduce benzene content; The method can be utilized catalytic cracking unit, makes full use of alcohol resource, and especially methyl alcohol is realized oil refining-chemical industry integrated in improving quality of gasoline, has a good application prospect.
Compared with prior art, the present invention has following technique effect:
(1), while adopting method provided by the present invention to process the gasoline that contains benzene, Determination of Benzene In Gasoline can decline up to more than 65 volume %.
(2), while adopting method provided by the present invention to process the gasoline that contains benzene, alcohol reacts and is converted into gasoline fraction with benzene, has increased gasoline yield.
(3), while adopting method provided by the present invention to process the gasoline that contains benzene, alcohol reacts and is converted into aromatic hydrocarbons with benzene, and gasoline octane rating is improved.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the catalysis conversion method of reduction benzene content in gasoline provided by the invention.
Embodiment
According to the present invention, although the number of reaction zone is The more the better, but reaction zone number is more, the structure of equipment is more complicated, thereby causes operation inconvenience, and cost is also corresponding to be increased to some extent, therefore can decide according to the requirement of falling benzene the number of required reaction zone, the present inventor's discovery, in the time requiring benzene content decline 50-80%, the number of reaction zone can be 4-8; In the time requiring benzene content to reduce 30-75%, the number of reaction zone can be 3-5; In the time requiring benzene content to reduce 10-66%, the number of reaction zone can be 2-3.Because in current domestic gasoline product, catalytically cracked gasoline ratio is about 80% (weight), in catalytically cracked gasoline, benzene content is approximately 0.5-1.3% (volume), EPA is in atmosphere Toxic rules (MAST) subordinate phase of motor vehicle emission, proposition will be reduced to 0.62% by average this content in the gasoline of the whole America in 2011, meet the demands as long as make benzene content in gasoline drop to, based on this, the preferred described reaction zone of the present invention is 2.
According to the present invention, as long as although realize the Contact Temperature of any one later reaction zone of the first reaction zone lower than the temperature of adjacent previous reaction zone, and the residence time of this reaction zone is longer than the residence time of adjacent previous reaction zone and can realizes object of the present invention, but the inventor finds, when the temperature of later any one reaction zone contact in described the first reaction zone than the adjacent low 30-300 in previous reaction zone ℃, the residence time of this reaction zone extends 0.5-15s than adjacent previous reaction zone simultaneously, falls benzene effect better; Further find, when the temperature of any one later reaction zone contact of described the first reaction zone than the adjacent low 50-250 in previous reaction zone ℃, the residence time of this reaction zone extends 1-10s than adjacent previous reaction zone simultaneously, falls benzene better effects if.According to the present invention, the temperature of described the first reaction zone contact can be generally 0.5-2.5s for 250-550 ℃, the residence time, and further preferably the temperature of contact is that 300-500 ℃, the residence time are 0.8-2.0s.
Multiple reaction zone of the present invention can be provided by least two kinds of combinations in fluidized-bed reactor, riser reactor, downstriker transfer limes reactor or three or a kind of at least two combination of reactors of reactor.The compound reactor that for example can adopt the compound reactor being made up of riser tube and fluidized-bed, the compound reactor being made up of riser tube and downstriker transfer limes, the compound reactor being made up of two or more riser tubes, the compound reactor being made up of two or more fluidized-beds, is made up of two or more downstriker transfer limess, above-mentioned every kind of reactor for example can be divided into multiple reaction zones by the reducing of reactor.That described fluidized-bed can be selected from is fixed fluidized bed, one or more in dispersion fluidized bed, bubbling bed, turbulent bed, fast bed, conveying bed, dense phase fluidized bed, preferably fluidized-bed, more preferably dense phase fluidized bed.Described riser tube can be selected from equal diameter riser tube, etc. linear speed riser tube, various one or more that straighten in the riser tube of footpath, preferably equal diameter riser tube.Although multiple reaction zone of the present invention can adopt the combination of at least two kinds of above-mentioned reactors or at least two of a kind of reactor to combine to realize, no matter be input cost and the various drain on manpower and material resources that the combination of two or more reactors or the combination of more than two reactor have increased equipment undoubtedly greatly.Therefore, under preferable case, realize in a reactor multiple reaction zone of the present invention, for example can in reducing fluidized-bed, reducing riser tube, reducing downstriker transfer limes reactor, realize, the present inventor finds, the present invention realizes by reducing riser reactor especially preferred multiple reaction zones, for example, in the time that reaction zone is 2, can be by along reactant flow direction, the riser tube that comprises the conversion zone that conversion zone that diameter is less and diameter are larger is realized, thereby forms the first reaction zone and second reaction zone.Can use the disclosed reducing riser tube of CN1237477A about this reducing riser tube.
According to the present invention, in order to obtain, benzene effect is better fallen, the present invention can also realize by improving later any one or more reaction zones, first reaction zone and the agent-oil ratio of first reaction zone, for example can in later any one or more reaction zones, first reaction zone, add catalyzer, the reaction zone that makes to add catalyzer than the agent weight of oil of adjacent last reaction zone than high 5-50%, further preferably, the reaction zone that makes to add catalyzer to the amount of adding catalyzer in later any one or more reaction zones, first reaction zone than the agent weight of oil of adjacent last reaction zone than high 10-40%, the catalyzer wherein adding can be live catalyst, regenerated catalyst, for the more effective catalyzer that utilizes, at least a portion of the catalyzer that the present invention preferably adds is regenerated catalyst.
The present inventor is unexpected discovery also, in order to obtain, benzene effect is better fallen, not only can realize by improving later any one or more reaction zones, first reaction zone and the agent-oil ratio of first reaction zone, and reduce a later reaction zone of the first reaction zone than the agent weight of oil ratio of adjacent last reaction zone, also can realize.For example can be by add gasoline and alcohol in later any one or more reaction zones, the first reaction zone, the reaction zone that makes to add gasoline and alcohol than the agent weight of oil of adjacent last reaction zone than low 10-50%.Further preferably, the reaction zone that makes to add gasoline and alcohol to the amount of adding gasoline and alcohol in later any one or more reaction zones, first reaction zone than the agent weight of oil of adjacent last reaction zone than low 20-40%.
According to the present invention, described dose of weight of oil is than being catalyzer and the weight ratio of the gasoline containing benzene, and the agent weight of oil ratio of described first reaction zone is generally 1-30: 1, and more preferably 5-20: 1.
According to the catalysis conversion method of reduction benzene content in gasoline provided by the invention, described alcohol is preferably monohydroxy-alcohol and/or the polyvalent alcohol that carbonatoms is 1-5.Described polyvalent alcohol can be one or more in dibasic alcohol, trivalent alcohol and tetravalent alcohol.Under preferable case, described alcohol is one or more in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, propylene glycol, glycerol, tetramethylolmethane.
Although a small amount of alcohol can be realized object of the present invention, under preferable case, in described the first reaction zone, alcohol is 0.01-1 with the weight ratio of the gasoline containing benzene: 1, and further preferred alcohols is 0.02-0.5 with the weight ratio of the gasoline containing benzene: 1.In above-mentioned preferable range, the reduction effect of benzene content is obvious especially.
The method according to this invention, described contact is carried out under pre-lift medium exists, described pre-lift medium can be various inert carrier gas flow, described inert gas flow can be the various gas streams that do not disturb benzene and alcohol reaction, for example, can be one or more in neutral element gas stream in water vapor stream, airflow, nitrogen gas stream and the periodic table of elements, be preferably water vapor stream.
In the present invention, the contact conditions of the reaction zone after described the first reaction zone and the first reaction zone, except the residence time and temperature, all the other contact conditions can be identical or different.Under preferable case, the condition of described the first reaction zone contact comprises that temperature of reaction is 250-550 ℃, the residence time is 0.5-2.5s, reaction pressure is the pressure that reaction mass self produces in reactor, be generally 0.1-1.0MPa, catalyzer is 1-30 with the weight ratio of the gasoline containing benzene: 1, water vapour is 0.05-1.0 with raw material weight ratio: 1, preferred reaction conditions is that temperature of reaction is 300-500 ℃, the residence time is 0.8-2.0s, reaction pressure is 0.1-0.8MPa, and catalyzer is 4-20 with the weight ratio of the gasoline containing benzene: 1.Further preferred reaction conditions is that temperature of reaction is 310-500 ℃, and the residence time is 1.0-2.0s, and reaction pressure is 0.2-0.6MPa, and catalyzer is 5-10 with the weight ratio of the gasoline containing benzene: 1.
The present inventor finds, in the time using molecular sieve as catalyzer, if reduce the catalyzed reaction of Determination of Benzene In Gasoline carries out in fixed-bed reactor or catalyticreactor, because the activity of catalyst molecule sieve is higher, deactivation rate is very fast, catalyzer needs frequent regeneration, in the operating process of fixed-bed reactor or catalyticreactor, catalyzer can not be changed, be difficult for realizing the regenerative process of catalyzer, and particle swarm in fluidized-bed has the character of class quasi-fluid, can from device, introduce, shift out, and can between two fluidized-beds, realize a large amount of circulations, this is achieved reaction-regenerative coupling process, be easier to apply in engineering as the easy decaying catalyst of this class of molecular sieve catalyst.
In order better to embody advantage of the present invention, the present invention preferably the content of the described Benzene In Gasoline containing benzene more than 0.5 % by weight, more than being preferably in 1.0 % by weight, for example 0.5-10 % by weight, preferably 1-5 % by weight.The described gasoline containing benzene can be selected from one or more the mixture in catalytic gasoline, reformed gasoline, straight-run spirit and coker gasoline, preferred catalytic gasoline.Above-mentioned gasoline fraction is that its full cut is or/and part narrow fraction.
In the present invention, described catalytic cracking catalyst can also contain zeolite and heat-resistant inorganic oxide, and described zeolite is mesopore and/or large pore zeolite.Take the total amount of described catalytic cracking catalyst as benchmark, the content of described zeolite is preferably 1-50 % by weight, and the content of described heat-resistant inorganic oxide is 50-99 % by weight.Further under preferable case, described catalytic cracking catalyst also contains the clay take the total amount of described catalytic cracking catalyst as benchmark 0-70 % by weight.
The present inventor finds, when containing more C in described gasoline
9-C
12when aromatic hydrocarbons, when described zeolite is the mixture of large pore zeolite or large pore zeolite and mesopore zeolite, the effect of falling benzene is made active ingredient catalytic cracking catalyst compared with mesopore zeolite is good a lot of in the situation that other conditions are identical.Fall the effect of benzene best be the mixture of large pore zeolite and mesopore zeolite.Therefore the mixture that, the preferred described zeolite of the present invention is large pore zeolite or large pore zeolite and mesopore zeolite.Further under preferable case, take the total amount of zeolite as benchmark, the content of described large pore zeolite is the heavy % of 20-100, and the content of described mesopore zeolite is 0-80 % by weight.More preferably in situation, take the total amount of zeolite as benchmark, the content of described large pore zeolite is the heavy % of 50-80, and the content of described mesopore zeolite is 20-50 % by weight.In above-mentioned preferable range, the content of Benzene In Gasoline can be even lower.
In the present invention, described mesopore zeolite and large pore zeolite are continued to use the definition of this area routine, i.e. the mean pore size 0.5-0.6nm of mesopore zeolite, the mean pore size 0.8-1.0nm of large pore zeolite.For example, described large pore zeolite can select the one or more of mixture in this group zeolite that super steady Y, high silicon Y that free Rare Earth Y (REY), rare earth hydrogen Y (REHY), the whole bag of tricks obtain form.
Described mesopore zeolite can be selected from ZSM series zeolite and/or ZRP zeolite, also can carry out modification to the transition metal such as the non-metallic elements such as phosphorus and/or iron, cobalt, nickel for above-mentioned mesopore zeolite, about the more detailed description of ZRP is referring to US5,232,675, ZSM series zeolite is selected from the one or more of mixture among the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures, about the more detailed description of ZSM-5 is referring to US3,702,886.
Described heat-resistant inorganic oxide can be the conventional various heat-resistant inorganic oxides that use of catalyst field, is preferably silicon-dioxide (SiO
2) and/or aluminium sesquioxide (Al
2o
3).
Described clay is as matrix (being carrier), can be the conventional various clays that use of catalyst field, for example described clay can be selected from one or more the mixture in kaolin, halloysite, polynite, wilkinite, sepiolite, diatomite, tired de-soil, preferably kaolin.
Under preferable case, method of the present invention also comprises that, by reacted catalyzer coke burning regeneration after stripping, the Returning reactor after cooling of the catalyzer after regeneration recycles, and catalyzer at least a portion of the present invention is the catalyzer after regeneration.The renovation process of catalyzer has been conventionally known to one of skill in the art, does not repeat them here.
Take reducing riser reactor as example, by reference to the accompanying drawings a kind of embodiment of method provided by the present invention is further detailed below, similarly, the present invention repeats no more in the combination of all the other the various reactors that can realize multiple reaction zones.
As shown in Figure 1, pre-lift medium is entered by riser reactor 2 bottoms through pipeline 1, from the regeneration catalyzing conversion catalyst of pipeline 16 under the castering action of pre-lift medium, move upward along riser tube, containing the gasoline of benzene and alcohol bottom the first reaction zone I of pipeline 3 and injecting lift pipe reactor 2 together with thinner (as atomizing steam) from pipeline 4, mix with the existing logistics of riser reactor 2, on hot catalyzer, there is cracking reaction containing the gasoline of benzene and the mixture of alcohol, and move upward and enter second reaction zone II and continue reaction, containing the gasoline of benzene and the mixture of alcohol (fresh or participate in the reacted gasoline of benzene and the mixture of alcohol of containing) and/or catalyzer (regenerator and/or fresh dose) through pipeline 5 the second reaction zone II with injecting lift pipe reactor 2 together with thinner (as atomizing steam) from pipeline 6, mix and contact with the logistics in the II of riser reactor second reaction zone, the oil gas generating and the reclaimable catalyst of inactivation enter the cyclonic separator in settling vessel 8 through pipeline 7, realize separating of reclaimable catalyst and oil gas, reaction oil gas enters collection chamber 9, catalyst fines returns to settling vessel 8 by dipleg, in settling vessel 8, reclaimable catalyst flows to stripping stage 10, contact with the gas stripping gas (steam) from pipeline 11.The oil gas going out from stripping reclaimable catalyst enters collection chamber 9 after cyclonic separator separates.Reclaimable catalyst after stripping enters revivifier 13 through inclined tube 12, main air enters revivifier 14 through pipeline 14, coke on burning-off reclaimable catalyst, make the reclaimable catalyst regeneration of inactivation, flue gas enters cigarette machine through pipeline 15, and the regenerated catalyst of high temperature returns to riser tube bottom cycle through regenerator sloped tube 16 and uses.Reaction product oil gas in collection chamber 9, through main oil gas piping 17, enters follow-up separation system.Described pre-lift medium can be dry gas, steam or their mixture.
The following examples will be further described present method, but therefore not limit the present invention.
Feedstock property used in embodiment is in table 1.
Embodiment 1
The present embodiment explanation adopts method provided by the invention.
Adopt the technique shown in Fig. 1, using the listed gasoline A containing benzene of table 1 as reaction raw materials, methyl alcohol (Beijing Chemical Plant, purity >=99.5%) as alkylating reagent, (character a) is made catalyzer in catalyzer in table 2 to use Y zeolite, at reducing riser tube, (the first reaction zone diameter of reducing riser tube is 0.25 meter, is highly 4 meters; Second reaction zone diameter is 1 meter, is highly 6.5 meters, and the first reaction zone is positioned at the bottom of second reaction zone, in following examples, if no special instructions, all adopts this reducing riser tube) in carry out the catalytic conversion reaction of gasoline and methyl alcohol, produce low benzoline.
200 ℃ of high-temperature vapors containing the gasoline A of benzene and the mixture of methyl alcohol and preheating are mixed in reducing riser tube the first reaction zone, it is 400 ℃ in the temperature of reaction of the first reaction zone, the weight ratio of catalyzer and liquid combined feed total feed is 15, methyl alcohol is 0.25: 1 with the weight ratio of the gasoline containing benzene, the residence time is 2s, water injection rate (accounting for liquid total feed) is after contacting with catalyzer under the condition of 5 % by weight, reactant flow enters second reaction zone and reacts, the temperature of second reaction zone is 200 ℃, and the residence time is 4s.After carrying out catalytic conversion reaction in the first reaction zone and second reaction zone, make low benzoline.Reaction product, steam and reclaimable catalyst separate in negative area, and reaction product isolated obtains gaseous product and product liquid, and reclaimable catalyst adopts water vapour stripping, and stripping goes out the hydrocarbon product adsorbing on reclaimable catalyst.Catalyzer after stripping contacts regeneration again with air, burn coke deposited on catalyst charcoal, and the catalyzer after regeneration turns back to reactor cycles and uses.
Operational condition and product distribute and list in table 3.As can be seen from Table 3, the volume content of Benzene In Gasoline is down to 0.54% by 0.85%, and benzene content has declined 36.49%.
Adopt the technique shown in Fig. 1, using the listed gasoline B containing benzene of table 1 as reaction raw materials, methyl alcohol (Beijing Chemical Plant, purity >=99.5%) as alkylating reagent, (character b) is made catalyzer in catalyzer in table 2 to use type ZSM 5 molecular sieve, in reducing riser tube, carry out the catalytic conversion reaction of gasoline and methyl alcohol, produce low benzoline.
Be mixed in reducing riser tube the first reaction zone containing the gasoline B of benzene and the mixture of methyl alcohol and the high-temperature vapor of preheating, it is 300 ℃ in the temperature of reaction of the first reaction zone, the weight ratio of catalyzer and liquid combined feed total feed is 6, methyl alcohol is 0.20: 1 with the weight ratio of the gasoline containing benzene, the residence time of liquid combined feed total feed is 2s, after contacting with catalyzer under the condition of water injection rate (accounting for liquid total feed) 10 % by weight, then reactant flow enters second reaction zone and reacts, the temperature of second reaction zone is 200 ℃, the residence time is 5s, the term harmonization of all the other and the first reaction zone.After carrying out catalytic conversion reaction in the first reaction zone and second reaction zone, make low benzoline.Reaction product, steam and reclaimable catalyst separate in negative area, and reaction product isolated obtains gaseous product and product liquid, and reclaimable catalyst adopts water vapour stripping, and stripping goes out the hydrocarbon product adsorbing on reclaimable catalyst.Catalyzer after stripping contacts regeneration again with air, burn coke deposited on catalyst charcoal, and the catalyzer after regeneration turns back to reactor cycles and uses.
Operational condition and product distribute and list in table 3.As can be seen from Table 3, the volume content of Benzene In Gasoline is down to 1.17% by 3.44%, and Determination of Benzene In Gasoline has declined 65.99%.
Adopt the technique shown in Fig. 1, using the listed gasoline C containing benzene of table 1 as reaction raw materials, methyl alcohol (Beijing Chemical Plant, purity >=99.5%) as alkylating reagent, (character b) is made catalyzer in catalyzer in table 2 to use type ZSM 5 molecular sieve, in reducing riser tube, carry out the catalytic conversion reaction of gasoline and methyl alcohol, produce low benzoline.
Be mixed in reducing riser tube the first reaction zone containing the gasoline C of benzene and the mixture of methyl alcohol and the high-temperature vapor of preheating, it is 500 ℃ in the temperature of reaction of the first reaction zone, the weight ratio of catalyzer and liquid combined feed total feed is 6, methyl alcohol is 0.125: 1 with the weight ratio of the gasoline containing benzene, the residence time of liquid combined feed total feed is 2s, after contacting with catalyzer under the condition of water injection rate (accounting for liquid total feed) 5 % by weight, then reactant flow enters second reaction zone and reacts, the temperature of second reaction zone is 350 ℃, the residence time is 4s, the term harmonization of all the other and the first reaction zone.After carrying out catalytic conversion reaction in the first reaction zone and second reaction zone, make low benzoline.Reaction product, steam and reclaimable catalyst separate in negative area, and reaction product isolated obtains gaseous product and product liquid, and reclaimable catalyst adopts water vapour stripping, and stripping goes out the hydrocarbon product adsorbing on reclaimable catalyst.Catalyzer after stripping contacts regeneration again with air, burn coke deposited on catalyst charcoal, and the catalyzer after regeneration turns back to reactor cycles and uses.
Operational condition and product distribute and list in table 3.As can be seen from Table 3, the volume content of Benzene In Gasoline is down to 0.99% by 1.85%, and Determination of Benzene In Gasoline has declined 46.49%.
Comparative example 1
Adopt the method for embodiment 3 to carrying out catalyzed conversion containing the gasoline of benzene, different, the first reaction zone of riser reactor is identical with the caliber of second reaction zone, and operational condition and product distribute as shown in table 3.
The volume content of Benzene In Gasoline is down to 1.09% by 1.85% as can be seen from Table 3, and Determination of Benzene In Gasoline has declined 41.08%.
Comparative example 2
Adopt the method for embodiment 3 to carry out catalyzed conversion to the gasoline containing benzene, different, operational condition and product distribute and list in table 3.As can be seen from Table 3, the volume content of Benzene In Gasoline is down to 1.26% by 1.85%, and Determination of Benzene In Gasoline has declined 31.89%.
Comparative example 3
Adopt the method for embodiment 3 to carry out catalyzed conversion to the gasoline containing benzene, different, described catalyzer is solid phosphoric acid catalyst (degree of crystallinity > 30%, Shenyang Runda Chemical Industry Co., Ltd.).Product distributes and lists in table 4.As can be seen from Table 4, the volume content of Benzene In Gasoline is down to 1.45% by 1.85%, and Determination of Benzene In Gasoline has declined 21.86%.
Comparative example 4
Adopt the method for embodiment 3 to carry out catalyzed conversion to the gasoline containing benzene, different, described catalyzer is that (character in catalyzer in table 2 e) for β zeolite.Product distributes and lists in table 4.As can be seen from Table 4, the volume content of Benzene In Gasoline is down to 1.13% by 1.85%, and Determination of Benzene In Gasoline has declined 38.70%.
Embodiment 4
Adopt the method for embodiment 3 to carry out catalyzed conversion to the gasoline containing benzene, different, by adding the catalyzer after regeneration to reaction 2nd district, the weight ratio that makes catalyzer and liquid combined feed total feed is 8.
Product distributes and lists in table 3.As can be seen from Table 3, the volume content of Benzene In Gasoline is down to 0.90% by 1.85%, and Determination of Benzene In Gasoline has declined 51.35%.
Embodiment 5
Adopt the method for embodiment 3 to carry out catalyzed conversion to the gasoline containing benzene, different, described containing the gasoline of benzene and the mixture of methyl alcohol by adding to reaction 2nd district, the weight ratio that makes catalyzer and liquid combined feed total feed is 4.
Product distributes and lists in table 3.As can be seen from Table 3, the volume content of Benzene In Gasoline is down to 0.95% by 1.85%, and Determination of Benzene In Gasoline has declined 48.65%.
Adopt the method for embodiment 3 to carry out catalyzed conversion to the gasoline containing benzene, different, methyl alcohol (Beijing Chemical Plant, purity >=99.5%) is replaced by ethylene glycol.
Product distributes and lists in table 4.As can be seen from Table 4, the volume content of Benzene In Gasoline is down to 1.07% by 1.85%, and Determination of Benzene In Gasoline has declined 42.11%.
Adopt the method for embodiment 3 to carry out catalyzed conversion to the gasoline containing benzene, different is, methyl alcohol is replaced by the mixture of ethanol (Beijing Chemical Plant, purity >=99.5%) and 1: 1 weight ratio of tetramethylolmethane (Beijing Chemical Plant, purity >=98%).
Product distributes and lists in table 4.As can be seen from Table 4, the volume content of Benzene In Gasoline is down to 1.09% by 1.85%, and Determination of Benzene In Gasoline has declined 41.14%.
Adopt the method for embodiment 3 to carry out catalyzed conversion to the gasoline containing benzene, different, contain the gasoline B of benzene as reaction raw materials.
Product distributes and lists in table 4.As can be seen from Table 4, the volume content of Benzene In Gasoline is down to 1.76% by 3.44%, and Determination of Benzene In Gasoline has declined 48.98%.
Adopt the method for embodiment 8 to carry out catalyzed conversion to the gasoline containing benzene, different, catalyzer is the c catalyzer shown in table 2.
Product distributes and lists in table 4.As can be seen from Table 4, the volume content of Benzene In Gasoline is down to 1.38% by 3.44%, and Determination of Benzene In Gasoline has declined 59.97%.
Adopt the method for embodiment 8 to carry out catalyzed conversion to the gasoline containing benzene, different, catalyzer is the d catalyzer shown in table 2.
Product distributes and lists in table 4.As can be seen from Table 4, the volume content of Benzene In Gasoline is down to 1.31% by 3.44%, and Determination of Benzene In Gasoline has declined 62.06%.
Table 1
| Numbering | A | B | C |
| Type of feed | Gasoline | Gasoline | Gasoline |
| Density (20 ℃), kg/m 3 | 736.3 | 786.2 | 722.9 |
| Octane value | |||
| RON | 91.9 | 97.4 | 89.7 |
| MON | 82.0 | 83.6 | 80.6 |
| Benzene, volume % | 0.85 | 3.44 | 1.85 |
| Alkene, volume % | 42.3 | 44.6 | 27.2 |
| C9-C12 aromatic hydrocarbons, volume % | 14.1 | 24.3 | 9.2 |
| Boiling range (℃) | |||
| Initial boiling point | 38 | 60 | 39 |
| 10％ | 61 | 82 | 51 |
| 50％ | 91 | 106 | 88 |
| 90％ | 143 | 166 | 157 |
| Final boiling point | 201 | 195 | 183 |
Table 2
Table 3
Table 4
Can find out from the result of table 3 and table 4, method provided by the invention can effectively reduce the benzene content in gasoline.By embodiment 1-3 and comparative example 1 and comparative example 2 contrasts can be found out, adopt method of the present invention, by making raw material through the reaction of multiple reaction zones, control the Contact Temperature of any one later reaction zone of the first reaction zone lower than the temperature of adjacent previous reaction zone, and the residence time of this reaction zone is longer than the residence time of adjacent previous reaction zone, benzene better effects if is fallen; By comparative example 4 and 5 and embodiment 3 known, to second reaction zone by adding catalyzer and/or adding the conversion that raw material is all more conducive to benzene, thereby can obtain the gasoline of lower benzene content; Simultaneously by embodiment 3 can be found out with comparative example 3-4 contrast, in reducing riser reactor, adopt active higher molecular sieve catalyst, in higher reaction temperatures with compared with under short residence time(SRT), not only can obviously reduce Determination of Benzene In Gasoline, can also obtain comparatively ideal product and distribute.Embodiment 8, embodiment 9 can be found out with embodiment 10 contrasts, as C in raw material
9-C
12when aromaticity content is higher, the molecular sieve catalyst molecular sieve catalyst less than mean pore size that mean pore size is larger is more conducive to reduce benzene content in gasoline, but in the time of the composite use of molecular sieve of different pore size size, reduction benzene content in gasoline effect is better.
Claims (20)
1. a catalysis conversion method that reduces benzene content in gasoline, is characterized in that, the method comprises and will contact in multiple reaction zones successively with catalytic cracking catalyst with alcohol containing the gasoline of benzene, isolates the gasoline of benzene content reduction in the mixture from contacting; Described multiple reaction zone comprises the later reaction zone in the first reaction zone and the first reaction zone, the Contact Temperature of later any one reaction zone, the first reaction zone is lower than the temperature of adjacent previous reaction zone, and the residence time of this reaction zone is longer than the residence time of adjacent previous reaction zone.
2. method according to claim 1, wherein, the number of reaction zone is 2.
3. method according to claim 1 and 2, wherein, the temperature of later any one reaction zone contact in the first reaction zone than the adjacent low 30-300 in previous reaction zone ℃, residence time of this reaction zone than adjacent previous reaction head of district 0.5-15s.
4. method according to claim 3, wherein, the temperature of later any one reaction zone contact in the first reaction zone than the adjacent low 50-250 in previous reaction zone ℃, residence time of this reaction zone than adjacent previous reaction head of district 1-10s.
5. method according to claim 1 and 2, wherein, multiple reaction zones are provided by least two kinds of combinations in fluidized-bed reactor, riser reactor, downstriker transfer limes reactor or three or a kind of at least two combination of reactors of reactor.
6. method according to claim 5, wherein, the number of reaction zone is 2, provided by a riser reactor, along the flow direction of reactant flow, the conversion zone of described riser reactor comprises conversion zone and the larger conversion zone of diameter that diameter is less, forms respectively the first reaction zone and second reaction zone.
7. method according to claim 1 and 2, wherein, the method also comprises in later any one or more reaction zones, first reaction zone adds catalyzer, the reaction zone that makes to add catalyzer than the agent weight of oil of adjacent last reaction zone than high 5-50%.
8. method according to claim 7, wherein, add the reaction zone of catalyzer than the agent weight of oil of adjacent last reaction zone than high 10-40%.
9. method according to claim 7, wherein, the method also comprises from reacted mixture isolates reclaimable catalyst, and reclaimable catalyst is regenerated; At least a portion of described catalyzer is the catalyzer after regeneration.
10. method according to claim 1 and 2, wherein, the method also comprises in later any one or more reaction zones, the first reaction zone adds gasoline and alcohol, the reaction zone that makes to add gasoline and alcohol than the agent weight of oil of adjacent last reaction zone than low 10-50%.
11. methods according to claim 10, wherein, the reaction zone of adding gasoline and alcohol than the agent weight of oil of adjacent last reaction zone than low 20-40%.
12. methods according to claim 1, wherein, the condition of the first reaction zone contact comprises that alcohol and the weight ratio of the gasoline containing benzene are 0.01-1: 1.
13. methods according to claim 12, wherein, the condition of the first reaction zone contact comprises that alcohol and the weight ratio of the gasoline containing benzene are 0.02-0.5: 1.
14. according to the method described in claim 1,2,12 or 13, wherein, the condition of the first reaction zone contact comprises that temperature of reaction is 250-550 ℃, and the residence time is 0.5-2.5s, reaction pressure is 0.1-1.0MPa, and catalyzer is 1-30 with the weight ratio of the gasoline containing benzene: 1.
15. methods according to claim 14, wherein, temperature of reaction is 300-500 ℃, and the residence time is 0.8-2.0s, and reaction pressure is 0.1-0.8MPa, and catalyzer is 4-20 with the weight ratio of the gasoline containing benzene: 1.
16. methods according to claim 1, wherein, alcohol is that carbonatoms is monohydroxy-alcohol and/or the polyvalent alcohol of 1-5.
17. methods according to claim 16, wherein, alcohol is one or more in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, propylene glycol, glycerol, tetramethylolmethane.
18. methods according to claim 1, wherein, catalytic cracking catalyst contains zeolite and heat-resistant inorganic oxide, and described zeolite is mesopore and/or large pore zeolite.
19. methods according to claim 1, wherein, containing the content of the Benzene In Gasoline of benzene more than 0.5 % by weight.
20. methods according to claim 1 and 2, wherein, the method also comprises from reacted mixture isolates reclaimable catalyst, and reclaimable catalyst is regenerated; At least a portion of described catalyzer is the catalyzer after regeneration.
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| US5865986A (en) * | 1994-09-28 | 1999-02-02 | Mobil Oil Corporation | Hydrocarbon conversion |
| CN101362964A (en) * | 2007-08-09 | 2009-02-11 | 中国石油化工股份有限公司 | Catalytic conversion method for reducing benzene content in gasoline |
| WO2009108655A2 (en) * | 2008-02-26 | 2009-09-03 | Catalytic Distillation Technologies | Process for benzene removal from gasoline |
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|---|---|---|---|---|
| US4950823A (en) * | 1989-07-03 | 1990-08-21 | Mobil Oil Corp. | Benzene upgrading reformer integration |
| US5082983A (en) * | 1990-09-14 | 1992-01-21 | Mobil Oil Corporation | Reduction of benzene content of reformate in a catalytic cracking unit |
| US5414172A (en) * | 1993-03-08 | 1995-05-09 | Mobil Oil Corporation | Naphtha upgrading |
| US5865986A (en) * | 1994-09-28 | 1999-02-02 | Mobil Oil Corporation | Hydrocarbon conversion |
| CN101362964A (en) * | 2007-08-09 | 2009-02-11 | 中国石油化工股份有限公司 | Catalytic conversion method for reducing benzene content in gasoline |
| WO2009108655A2 (en) * | 2008-02-26 | 2009-09-03 | Catalytic Distillation Technologies | Process for benzene removal from gasoline |
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