CN102417829A - 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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- CN102417829A CN102417829A CN201110064391XA CN201110064391A CN102417829A CN 102417829 A CN102417829 A CN 102417829A CN 201110064391X A CN201110064391X A CN 201110064391XA CN 201110064391 A CN201110064391 A CN 201110064391A CN 102417829 A CN102417829 A CN 102417829A
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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 benzene content in the gasoline.
Background technology
Important component part as the tail gas pollution of motor-driven vehicle comprehensive regulation; Reduce content of sulfur in gasoline; Improve aromatic hydrocarbons and olefin(e) centent in the gasoline, improving constantly quality of gasoline has been the instant task that petroleum chemical industry faces, and especially the benzene in the gasoline is a kind of carcinogenic substance; In gasoline, can cause severe contamination to atmosphere through evaporation and incomplete combustion, there is strict restriction countries in the world to benzene content in the gasoline.World fuel standard II class specification index and Europe are limited to 1.0 volume %s in the requirement of benzene content in the EUROIII Emission Standard of implementing in 2000, the Europe IV standard implemented in 2005 in to motor spirit.EPA in atmosphere Toxic rules (MAST) subordinate phase of motor vehicle emission, further proposition will 2011 with the whole America gasoline in average benzene content be reduced to 0.62 volume %.China will implement in full the quality index (GB17930-2006) of motor spirit state III before 31 days December in 2009, require that aromaticity content is not more than 40% (volume) in the gasoline, and benzene content is not more than 1.0 volume %.In the domestic gasoline product, the catalytically cracked gasoline ratio is about 80 weight %, and benzene content is approximately 0.5%-1.3 volume % in the catalytically cracked gasoline.Therefore, benzene content just becomes the petroleum chemical industry urgent problem in the reduction gasoline.
Reduce that benzene content has following several method in the gasoline: saturated, isomerizing, benzene extracting, absorption method and alkylation.Preceding two kinds of methods all need consume hydrogen, owing to contain a large amount of alkene in the catalytically cracked gasoline, thereby the hydrogenation de-benzene process is not suitable for catalytically cracked gasoline; Benzene removes common employing aromatic hydrocarbons extraction technique in the gasoline; And benzene content is lower in the catalytically cracked gasoline, adopts the aromatic hydrocarbons extraction technique, causes operation easier and running cost to increase considerably; From economic angle, it is unaccommodated adopting the aromatic hydrocarbons extraction technique to reduce the FCC benzene content in gasoline; Absorption method is to utilize benzene in the specific sorbent material selective adsorption gasoline; This method shortcoming is loss yield of gasoline and high-octane number component; Because the loading capacity of sorbent material is limited, the competitive adsorption of benzene and other polar compound such as alkene, other aromatic hydrocarbons has a strong impact on adsorption efficiency; Unique conversion benzene and do not consume hydrogen, the technology of not losing octane value is the benzene alkylation technology.
US4827069 discloses a kind of technology that reduces benzene content in the gasoline; This technology is carried out the cut cutting with heavy petrol or catalytically cracked gasoline; And its rich benzene cut mixed with olefin feedstocks such as ethene, propylene, under the effect of solid acid catalyst, the alkylated reaction of alkene and benzene takes place.This process using dense, fluidized bed bioreactor, catalyzer is based on the shape-selective catalyst of ZSM-5 family, and the reaction of benzene and light olefin forms high-octane alkyl mononuclear aromatics in the gasoline.On this basis, US4975179 further discloses and has utilized middle above alkene of C5 of gasoline fraction (petroleum naphtha) and benzene that alkylating technology takes place, and can the benzene in the FCC gasoline be converted into high-octane korenyl, and still stay in the gasoline.Like this, can play the purpose that reduces benzene content in gasoline and increase gasoline octane rating, and the total aromaticity content in the gasoline changes not quite.
CN101372441A discloses a kind of employing fixed bed or fluidized-bed; The method of utilizing benzene and alkylation catalyst contact reacts in ethene and the gasoline to generate ethylbenzene reduces benzene content in the gasoline; Alkylation catalyst is a ZSM-5/ZSM-11 cocrystallization Si-Al zeolite; Be characterized in that low-concentration ethane need not purify, the gasoline that contains benzene that contains benzene is without dehydration, and the benzene transformation efficiency is greater than 45% in the gasoline.
WO9853029 discloses a kind of method that reduces benzene and sulphur content in the gasoline simultaneously.Sour gasoline and the cut that is rich in benzene are through two step process processes; At first be gasoline and the cut that is rich in benzene reacts selecting on the shape an acidic catalyst; Gasoline olefin and benzene generate alkylaromatic hydrocarbon with other aromatic hydrocarbons generation alkylated reaction in this process, and the reactant of generation is converted into H through hydrotreatment with the sulfocompound in the gasoline
2S.This method not only can reduce content of sulfur in gasoline, and can reduce benzene content in gasoline, and benzene content in gasoline descends about 20%.
CN1219026C discloses the full cut of a kind of catalytically cracked gasoline or lighting end and reformed gasoline by weight 1: 1-3: 1 mixes, and on the ultrafine particle zeolite alkylated catalyst, carries out the method that alkylated reaction reduces benzene content in the gasoline.This ultrafine particle zeolite aromatized catalyst total acid content is low, and especially L acid is lower, and the duct is more unimpeded, and alkene and benzene content are low in the clean gasoline of production.
US5491270 discloses a kind of method that is rich in benzoline benzene and macromole olefin alkylation; The gasoline that this method will contain benzene with contain than the gasoline of macromole (greater than C5) alkene with contain ZSM-5 sieve catalyst contact reacts, or be rich in benzene, alkene (greater than C5) simultaneously and contain ZSM-5 sieve catalyst contact reacts.The characteristics of this process are to be rich in benzoline and C5 alkene carries out alkylation, and the product that obtains mainly is the C10 alkylaromatic hydrocarbon.Benzene content reduces by 25 weight % at least in this process, and the C5 olefin(e) centent has reduced by 60 weight %.
US5120890 discloses a kind of petroleum naphtha and alkylating reagent that contains benzene and/or toluene and has carried out the process that liquid-phase alkylation reaches reduction benzene content boosting of octane rating.Alkylating reagent can with in the form injecting reactor of multistage with the transformation efficiency avoiding side reaction and reach benzene more than 70%.Alkylating reagent comprises ethene, propylene, butylene, methyl alcohol and ethanol.Catalyzer is a solid phosphoric acid catalyst.
Can reduce benzene content though adopt alkylation to fall the benzene technological line; But often need introduce the low-carbon alkene such as ethene, propylene of high value; Subsequent separation process is complicated, and facility investment increases, and during 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 satisfy the gasoline quality standard of increasingly stringent, be necessary to develop and a kind ofly reduce in the gasoline benzene content significantly and don't influence quality of gasoline and the method for yield.
Summary of the invention
The objective 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 the gasoline that contains benzene is contacted at a plurality of reaction zones with catalytic cracking catalyst with alcohol successively, from post reaction mixture, isolates the gasoline of benzene content reduction; Said a plurality of reaction zone comprises first reaction zone and the later reaction zone of first reaction zone; The contact temperature of any reaction zone that first reaction zone is later 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 through in gasoline, mixing a certain amount of alcohol, utilizes the alcohol and the alkylated reaction of benzene to reduce benzene content in the gasoline, improves quality of gasoline simultaneously; Through containing benzoline and catalytic cracking catalyst, further reduced benzene content successively through a plurality of reaction zones that temperature reduces gradually, the residence time prolongs gradually; This method CCU capable of using makes full use of pure resource, and especially methyl alcohol realizes that when improving quality of gasoline oil refining-chemical industry is integrated, has a good application prospect.
Compared with prior art, the present invention has following technique effect:
(1) adopt method provided by the present invention to handle when containing the gasoline of benzene, benzene content can descend up to more than the 65 volume % in the gasoline.
(2) adopt method provided by the present invention to handle when containing the gasoline of benzene, alcohol is gasoline fraction with the benzene reaction conversion, has increased gasoline yield.
(3) adopt method provided by the present invention to handle when containing the gasoline of benzene, alcohol is aromatic hydrocarbons with the benzene reaction conversion, and gasoline octane rating is improved.
Description of drawings
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, the reaction zone number is many 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 the number of required reaction zone according to the requirement of falling benzene; Contriver of the present invention finds that when requiring benzene content decline 50-80%, the number of reaction zone can be 4-8; When requiring benzene content to reduce 30-75%, the number of reaction zone can be 3-5; When requiring benzene content to reduce 10-66%, the number of reaction zone can be 2-3.Because in the present domestic gasoline product; The catalytically cracked gasoline ratio is about 80% (weight), and benzene content is approximately 0.5-1.3% (volume) in the catalytically cracked gasoline, and EPA is in atmosphere Toxic rules (MAST) subordinate phase of motor vehicle emission; Proposition will 2011 with the whole America gasoline in average this content be reduced to 0.62%; Meet the demands as long as benzene content in gasoline is dropped to, based on this, the preferred said reaction zone of the present invention is 2.
According to the present invention; Although be lower than the temperature of adjacent previous reaction zone as long as realize the contact temperature of any reaction zone that first reaction zone is later; And the residence time of this reaction zone is longer than the residence time of adjacent previous reaction zone and can realizes the object of the invention; But the inventor finds; When the temperature of the later any reaction zone contact of said first reaction zone than low 30-300 ℃ of adjacent previous reaction zone, residence time of this reaction zone is than adjacent previous reaction zone prolongation 0.5-15s simultaneously, it is better to fall the benzene effect; Further find, when the temperature of the later any reaction zone contact of said first reaction zone than low 50-250 ℃ of adjacent previous reaction zone, residence time of this reaction zone is fallen the benzene better effects if than adjacent previous reaction zone prolongation 1-10s simultaneously.According to the present invention, the temperature of said first reaction zone contact can be 0.5-2.5s for 250-550 ℃, the residence time generally, and further the temperature of preferred contact is that 300-500 ℃, the residence time are 0.8-2.0s.
A plurality of reaction zone of the present invention can be provided by at least two combination of reactors of two kinds among fluidized-bed reactor, riser reactor, downstriker transfer limes reactor drum or three combinations or a kind of reactor drum at least.The compound reactor that for example can adopt the compound reactor that constitutes by riser tube and fluidized-bed, constitute by riser tube and downstriker transfer limes, the compound reactor that constitutes by two or more riser tubes, the compound reactor that constitutes by two or more fluidized-beds, by the compound reactor that two or more downstriker transfer limess constitute, above-mentioned every kind of reactor drum for example can be divided into a plurality of reaction zones through the reducing of reactor drum.That said fluidized-bed can be selected from is fixed fluidized bed, in the dispersion fluidized bed, bubbling bed, turbulent bed, fast bed, Transport Bed, dense phase fluidized bed one or more, preferred fluidized-bed, more preferably dense phase fluidized bed.Said riser tube can be selected from the equal diameter riser tube, etc. in linear speed riser tube, the various change diameter riser tube one or more, preferred equal diameter riser tube.Though a plurality of reaction zone of the present invention can adopt combination or a kind of reactor drum at least two of at least two kinds of above-mentioned reactor drums to make up and realize, no matter is the combination of two or more reactor drums or input cost and the various drain on manpower and material resources that the combination of two above reactor drums has increased equipment undoubtedly greatly.Therefore, under the preferable case, a plurality of reaction zones according to the invention are realized in a reactor drum; For example can in reducing fluidized-bed, reducing riser tube, reducing downstriker transfer limes reactor drum, realize; Contriver of the present invention finds, the especially preferred a plurality of reaction zones of the present invention realize through the reducing riser reactor, for example; When reaction zone is 2; Can be by along the reactant flow direction, comprise that the riser tube of the conversion zone that conversion zone that diameter is less and diameter are bigger is realized, thereby form 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 better to fall the benzene effect; The present invention can also realize through improving the later any one or more reaction zones of first reaction zone and the agent-oil ratio of first reaction zone; For example can in the later any one or more reaction zones of first reaction zone, add catalyzer, the reaction zone that make to add catalyzer than the agent weight of oil of adjacent last reaction zone than high 5-50%, further preferred; The amount of in the later any one or more reaction zones of first reaction zone, adding catalyzer make the reaction zone that adds catalyzer than the agent weight of oil of adjacent last reaction zone than high 10-40%; The catalyzer that wherein adds can be live catalyst, regenerated catalyst, and for the more efficient use catalyzer, at least a portion of the catalyzer that the present invention preferably adds is a regenerated catalyst.
Contriver of the present invention is also unexpected to be found; In order to obtain better to fall the benzene effect; Not only can realize through improving the later any one or more reaction zones of first reaction zone and the agent-oil ratio of first reaction zone; And reduce the agent weight of oil ratio of a later reaction zone of first reaction zone than adjacent last reaction zone, also can realize.For example can through in the later any one or more reaction zones of first reaction zone, add gasoline and alcohol, make the reaction zone that adds gasoline and alcohol than the agent weight of oil of adjacent last reaction zone than low 10-50%.Further preferred, the amount of in the later any one or more reaction zones of first reaction zone, adding gasoline and alcohol make the reaction zone that adds gasoline and alcohol than the agent weight of oil of adjacent last reaction zone than low 20-40%.
According to the present invention, said dose of weight of oil is than being catalyzer and the weight ratio that contains the gasoline of benzene, and the agent weight of oil ratio of said first reaction zone is generally 1-30: 1, further be preferably 5-20: 1.
According to the catalysis conversion method of reduction benzene content in gasoline provided by the invention, said alcohol is preferably monohydroxy-alcohol and/or the polyvalent alcohol that carbonatoms is 1-5.Said polyvalent alcohol can be one or more in divalent alcohol, trivalent alcohol and the tetravalent alcohol.Under the preferable case, said alcohol is one or more in methyl alcohol, ethanol, propyl alcohol, terepthaloyl moietie, Ucar 35, USP Kosher, the tetramethylolmethane.
Although a spot of alcohol can be realized the object of the invention, under the preferable case, alcohol is 0.01-1 with the weight ratio that contains the gasoline of benzene in said first reaction zone: 1, and further alcohols is 0.02-0.5 with the weight ratio that contains the gasoline of benzene: 1.In above-mentioned preferable range, the reduction effect of benzene content is obvious especially.
According to the method for the invention; Said contact is being carried out in the presence of the lifting medium in advance; Said preparatory lifting medium can be various inert carrier gas flow, and said 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 the neutral element gas stream in water vapor stream, airflow, nitrogen gas stream and the periodic table of elements, be preferably water vapor stream.
Among the present invention, the contact conditions of the reaction zone after said first reaction zone and first reaction zone, except that the residence time and temperature, all the other contact conditions can be identical or different.Under the preferable case, the condition of said first reaction zone contact comprises that temperature of reaction is 250-550 ℃, and the residence time is 0.5-2.5s; Reaction pressure is the pressure that reaction mass self produces in reactor drum; Be generally 0.1-1.0MPa, catalyzer is 1-30 with the weight ratio that contains the gasoline of benzene: 1, and water vapour is 0.05-1.0 with the raw material weight ratio: 1; Preferred reaction conditions is that temperature of reaction is 300-500 ℃; 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 that contains the gasoline of 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 that contains the gasoline of benzene: 1.
Contriver of the present invention finds, when using molecular sieve as catalyzer, carries out in fixed-bed reactor or catalyticreactor if reduce the catalyzed reaction of benzene content in the gasoline; Because the catalyst molecule sieve is active higher; Deactivation rate is very fast, and catalyzer needs frequent regeneration, and catalyzer can not be changed in the operating process of fixed-bed reactor or catalyticreactor; Be difficult for realizing the regenerative process of catalyzer; And the particle swarm in the fluidized-bed has similar fluidic character, can from device, introduce, shift out, and can between two fluidized-beds, realize a large amount of circulations; This makes that reaction-regeneration coupling process is achieved, and is easier to use in engineering like the easy decaying catalyst of this type of sieve catalyst.
In order better to embody advantage of the present invention, the content that the present invention is preferred said to contain benzene in the gasoline of benzene is preferably in more than the 1.0 weight % more than 0.5 weight %, 0.5-10 weight % for example, preferred 1-5 weight %.The said gasoline that contains benzene can be selected from one or more the mixture in catalytic gasoline, reformed gasoline, straight-run spirit and the coker gasoline, preferred catalytic gasoline.Above-mentioned gasoline fraction is that its full cut is or/and the part narrow fraction.
Among the present invention, said catalytic cracking catalyst can also contain zeolite and heat-resistant inorganic oxide, and said zeolite is mesopore and/or large pore zeolite.Total amount with said catalytic cracking catalyst is a benchmark, and the content of said zeolite is preferably 1-50 weight %, and the content of said heat-resistant inorganic oxide is 50-99 weight %.Further under the preferable case, the total amount that said catalytic cracking catalyst also contains with said catalytic cracking catalyst is the clay of benchmark 0-70 weight %.
Contriver of the present invention finds, in said gasoline, contains more C
9-C
12During aromatic hydrocarbons, when said zeolite was the mixture of large pore zeolite or large pore zeolite and mesopore zeolite, the effect of falling benzene is made active ingredient than mesopore zeolite catalytic cracking catalyst was good a lot of under the identical situation of other conditions.Fall the effect of benzene best be the mixture of large pore zeolite and mesopore zeolite.Therefore, the preferred said zeolite of the present invention mixture that is large pore zeolite or large pore zeolite and mesopore zeolite.Further under the preferable case, be benchmark with the total amount of zeolite, the content of said large pore zeolite is the heavy % of 20-100, and the content of said mesopore zeolite is 0-80 weight %.More preferably under the situation, be benchmark with the total amount of zeolite, the content of said large pore zeolite is the heavy % of 50-80, and the content of said mesopore zeolite is 20-50 weight %.In above-mentioned preferable range, the content of benzene can fall lowlyer in the gasoline.
Among the present invention, said mesopore zeolite and large pore zeolite are continued to use the conventional definition in this area, 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, said large pore zeolite can be selected from a kind of or more kinds of mixture in this group zeolite that the ultra steady Y that is obtained by Rare Earth Y (REY), rare earth hydrogen Y (REHY), the whole bag of tricks, high silicon Y constitute.
Said mesopore zeolite can be selected from ZSM series zeolite and/or ZRP zeolite; Also can carry out modification with transition metals such as non-metallic elements such as phosphorus and/or iron, cobalt, nickel to above-mentioned mesopore zeolite; The more detailed description of relevant ZRP is referring to US5, and 232,675; The ZSM series zeolite is selected from a kind of or more kinds of mixture among the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures; The more detailed description of relevant ZSM-5 is referring to US3, and 702,886.
Said 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).
Said clay is as matrix (being carrier); Can be the conventional various clays that use of catalyst field; For example said clay can be selected from kaolin, halloysite, polynite, wilkinite, sepiolite, zeyssatite, tired one or more the mixture that takes off in the soil, preferred kaolin.
Under the preferable case, method of the present invention comprises that also with reacted catalyzer coke burning regeneration behind stripping, the Returning reactor after cooling off of the catalyzer after the regeneration recycles, and catalyzer at least a portion of the present invention is the catalyzer after regenerating.The renovation process of catalyzer has been conventionally known to one of skill in the art, repeats no more at this.
Be example with the reducing riser reactor below, a kind of embodiment of method provided by the present invention further explained in conjunction with accompanying drawing, all the other are various can realize a plurality of reaction zones reactor drum combination similarly, the present invention repeats no more.
As shown in Figure 1; Promoting medium is in advance got into by riser reactor 2 bottoms through pipeline 1; Regeneration catalyzing conversion catalyst from pipeline 16 is promoting under the castering action of medium in advance; Move upward along riser tube, the gasoline that contains benzene and alcohol, mix with riser reactor 2 existing logistics with bottom the first reaction zone I of thinner (like atomizing steam) the injecting lift pipe reactor 2 of pipeline 4 through pipeline 3; Cracking reaction takes place with pure mixture in the gasoline that contains benzene on the catalyzer of heat; And move upward and get into the second reaction zone II and continue reaction, contain the gasoline of benzene with 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 the pipeline 5 and the second reaction zone II, with logistics mixing in the riser reactor second reaction zone II and contact from thinner (like atomizing steam) the injecting lift pipe reactor 2 of pipeline 6; The cyclonic separator that the oil gas that generates and the reclaimable catalyst of inactivation get in the settling vessel 8 through pipeline 7; The realization reclaimable catalyst separates with oil gas, and reaction oil gas gets into collection chamber 9, and catalyst fines returns settling vessel 8 by dipleg; Reclaimable catalyst flows to stripping stage 10 in the settling vessel 8, contacts with gas stripping gas (steam) from pipeline 11.The oil gas that stripping goes out from reclaimable catalyst gets into collection chamber 9 after cyclonic separator separates.Reclaimable catalyst behind the stripping gets into revivifier 13 through inclined tube 12; Main air gets into revivifier 14 through pipeline 14; Coke on the burning-off reclaimable catalyst; Make the reclaimable catalyst regeneration of inactivation, flue gas gets into the cigarette machine through pipeline 15, and the pyritous regenerated catalyst returns the riser tube bottom cycle through regenerator sloped tube 16 and uses.Reaction product oil gas in the collection chamber 9 gets into follow-up separation system through main oil gas piping 17.Said preparatory lifting medium can be dry gas, steam or their mixture.
Following embodiment will further explain present method, but therefore not limit the present invention.
Feedstock property used among the embodiment is seen table 1.
Embodiment 1
Method provided by the invention is adopted in the present embodiment explanation.
Adopt technology shown in Figure 1; With the listed gasoline A that contains benzene of table 1 as reaction raw materials; Methyl alcohol (Beijing Chemical Plant, purity >=99.5%) is as alkylating reagent, and (character sees in the table 2 that catalyzer a) makes catalyzer to use Y zeolite; (first reaction zone diameter of reducing riser tube is 0.25 meter, highly is 4 meters at the reducing riser tube; Second reaction zone diameter is 1 meter, highly is 6.5 meters, and first reaction zone is positioned at the bottom of second reaction zone, if no special instructions, all adopts this reducing riser tube in following examples) in carry out the catalytic conversion reaction of gasoline and methyl alcohol, produce low benzoline.
Containing the gasoline A of benzene and 200 ℃ of high-temperature vapors of methanol mixture and preheating is mixed in reducing riser tube first reaction zone; Temperature of reaction at first reaction zone is 400 ℃; The weight ratio of catalyzer and liquid combined feed total feed is 15, and methyl alcohol is 0.25: 1 with the weight ratio that contains the gasoline of benzene, and the residence time is 2s; Water injection rate (accounting for the liquid total feed) is with after catalyzer contacts under the condition of 5 weight %; Reactant flow gets into second reaction zone and reacts, and the temperature of second reaction zone is 200 ℃, and the residence time is 4s.Through after first reaction zone and second reaction zone carry out catalytic conversion reaction, making low benzoline.Reaction product, steam and reclaimable catalyst separate in the negative area, and reaction product isolated obtains gaseous product and product liquid, and reclaimable catalyst adopts the water vapour stripping, and stripping goes out the hydrocarbon product that adsorbs on the reclaimable catalyst.Catalyzer behind the stripping contacts regeneration again with air, burn the coke deposited on catalyst charcoal, and the catalyzer after the regeneration turns back to reactor cycles and uses.
Operational condition and product distribute and list in table 3.Can be found out that by table 3 volume content of benzene reduces to 0.54% by 0.85% in the gasoline, benzene content has descended 36.49%.
Adopt technology shown in Figure 1; With the listed gasoline B that contains benzene of table 1 as reaction raw materials; Methyl alcohol (Beijing Chemical Plant, purity >=99.5%) uses type ZSM 5 molecular sieve (character is seen catalyzer b in the table 2) to make catalyzer as alkylating reagent; In the reducing riser tube, carry out the catalytic conversion reaction of gasoline and methyl alcohol, produce low benzoline.
Containing the gasoline B of benzene and the high-temperature vapor of methanol mixture and preheating is mixed in reducing riser tube first reaction zone; Temperature of reaction at first reaction zone is 300 ℃, and the weight ratio of catalyzer and liquid combined feed total feed is 6, and methyl alcohol is 0.20: 1 with the weight ratio that contains the gasoline of benzene; The residence time of liquid combined feed total feed is 2s; With after catalyzer contacts, reactant flow gets into second reaction zone and reacts then under the condition of water injection rate (accounting for the liquid total feed) 10 weight %, and the temperature of second reaction zone is 200 ℃; The residence time is 5s, the term harmonization of all the other and first reaction zone.Through after first reaction zone and second reaction zone carry out catalytic conversion reaction, making low benzoline.Reaction product, steam and reclaimable catalyst separate in the negative area, and reaction product isolated obtains gaseous product and product liquid, and reclaimable catalyst adopts the water vapour stripping, and stripping goes out the hydrocarbon product that adsorbs on the reclaimable catalyst.Catalyzer behind the stripping contacts regeneration again with air, burn the coke deposited on catalyst charcoal, and the catalyzer after the regeneration turns back to reactor cycles and uses.
Operational condition and product distribute and list in table 3.Can be found out that by table 3 volume content of benzene reduces to 1.17% by 3.44% in the gasoline, benzene content has descended 65.99% in the gasoline.
Embodiment 3
Adopt technology shown in Figure 1; With the listed gasoline C that contains benzene of table 1 as reaction raw materials; Methyl alcohol (Beijing Chemical Plant, purity >=99.5%) uses type ZSM 5 molecular sieve (character is seen catalyzer b in the table 2) to make catalyzer as alkylating reagent; In the reducing riser tube, carry out the catalytic conversion reaction of gasoline and methyl alcohol, produce low benzoline.
Containing the gasoline C of benzene and the high-temperature vapor of methanol mixture and preheating is mixed in reducing riser tube first reaction zone; Temperature of reaction at first reaction zone is 500 ℃, and the weight ratio of catalyzer and liquid combined feed total feed is 6, and methyl alcohol is 0.125: 1 with the weight ratio that contains the gasoline of benzene; The residence time of liquid combined feed total feed is 2s; With after catalyzer contacts, reactant flow gets into second reaction zone and reacts then under the condition of water injection rate (accounting for the liquid total feed) 5 weight %, and the temperature of second reaction zone is 350 ℃; The residence time is 4s, the term harmonization of all the other and first reaction zone.Through after first reaction zone and second reaction zone carry out catalytic conversion reaction, making low benzoline.Reaction product, steam and reclaimable catalyst separate in the negative area, and reaction product isolated obtains gaseous product and product liquid, and reclaimable catalyst adopts the water vapour stripping, and stripping goes out the hydrocarbon product that adsorbs on the reclaimable catalyst.Catalyzer behind the stripping contacts regeneration again with air, burn the coke deposited on catalyst charcoal, and the catalyzer after the regeneration turns back to reactor cycles and uses.
Operational condition and product distribute and list in table 3.Can be found out that by table 3 volume content of benzene reduces to 0.99% by 1.85% in the gasoline, benzene content has descended 46.49% in the gasoline.
Comparative Examples 1
Adopt the method for embodiment 3 that the gasoline that contains benzene is carried out catalyzed conversion, different is that first reaction zone of riser reactor is identical with the caliber of second reaction zone, and operational condition is as shown in table 3 with the product distribution.
Can be found out that by table 3 volume content of benzene in the gasoline reduces to 1.09% by 1.85%, benzene content has descended 41.08% in the gasoline.
Comparative Examples 2
Adopt the method for embodiment 3 that the gasoline that contains benzene is carried out catalyzed conversion, different is that operational condition and product distribute and list in table 3.Can be found out that by table 3 volume content of benzene reduces to 1.26% by 1.85% in the gasoline, benzene content has descended 31.89% in the gasoline.
Comparative Examples 3
Adopt the method for embodiment 3 that the gasoline that contains benzene is carried out catalyzed conversion, different is that said catalyzer is solid phosphoric acid catalyst (percent crystallinity＞30%, Shenyang Runda Chemical Industry Co., Ltd.).Product distributes and lists in table 4.Can be found out that by table 4 volume content of benzene reduces to 1.45% by 1.85% in the gasoline, benzene content has descended 21.86% in the gasoline.
Comparative Examples 4
Adopt the method for embodiment 3 that the gasoline that contains benzene is carried out catalyzed conversion, different is that said catalyzer is β zeolite (character is seen catalyzer e in the table 2).Product distributes and lists in table 4.Can be found out that by table 4 volume content of benzene reduces to 1.13% by 1.85% in the gasoline, benzene content has descended 38.70% in the gasoline.
Adopt the method for embodiment 3 that the gasoline that contains benzene is carried out catalyzed conversion, different is that the catalyzer through after adding regeneration to reaction two districts makes that the weight ratio of catalyzer and liquid combined feed total feed is 8.
Product distributes and lists in table 3.Can be found out that by table 3 volume content of benzene reduces to 0.90% by 1.85% in the gasoline, benzene content has descended 51.35% in the gasoline.
Adopt the method for embodiment 3 that the gasoline that contains benzene is carried out catalyzed conversion, different is through adding said gasoline and the methanol mixture that contains benzene to reaction two districts, to make that the weight ratio of catalyzer and liquid combined feed total feed is 4.
Product distributes and lists in table 3.Can be found out that by table 3 volume content of benzene reduces to 0.95% by 1.85% in the gasoline, benzene content has descended 48.65% in the gasoline.
Adopt the method for embodiment 3 that the gasoline that contains benzene is carried out catalyzed conversion, different is that methyl alcohol (Beijing Chemical Plant, purity >=99.5%) is replaced by terepthaloyl moietie.
Product distributes and lists in table 4.Can be found out that by table 4 volume content of benzene reduces to 1.07% by 1.85% in the gasoline, benzene content has descended 42.11% in the gasoline.
Adopt the method for embodiment 3 that the gasoline that contains benzene is carried out catalyzed conversion, different is that 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.Can be found out that by table 4 volume content of benzene reduces to 1.09% by 1.85% in the gasoline, benzene content has descended 41.14% in the gasoline.
Adopt the method for embodiment 3 that the gasoline that contains benzene is carried out catalyzed conversion, different is that the gasoline B that contains benzene is as reaction raw materials.
Product distributes and lists in table 4.Can be found out that by table 4 volume content of benzene reduces to 1.76% by 3.44% in the gasoline, benzene content has descended 48.98% in the gasoline.
Adopt the method for embodiment 8 that the gasoline that contains benzene is carried out catalyzed conversion, different is that catalyzer is the c catalyzer shown in the table 2.
Product distributes and lists in table 4.Can be found out that by table 4 volume content of benzene reduces to 1.38% by 3.44% in the gasoline, benzene content has descended 59.97% in the gasoline.
Adopt the method for embodiment 8 that the gasoline that contains benzene is carried out catalyzed conversion, different is that catalyzer is the d catalyzer shown in the table 2.
Product distributes and lists in table 4.Can be found out that by table 4 volume content of benzene reduces to 1.31% by 3.44% in the gasoline, benzene content has descended 62.06% in the gasoline.
Table 1
| Numbering | A | B | C |
| Type of feed | Gasoline | Gasoline | Gasoline |
| Density (20 ℃), kilogram/rice 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 (℃) | |||
| Over 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 that from the result of table 3 and table 4 method provided by the invention can effectively reduce the benzene content in the gasoline.Through embodiment 1-3 and Comparative Examples 1 are contrasted and can find out with Comparative Examples 2; Adopt method of the present invention; Through making raw material through a plurality of reaction zone reactions; The contact temperature of controlling the later any reaction zone of first reaction zone is lower than the temperature of adjacent previous reaction zone, and the residence time of this reaction zone be longer than the residence time of adjacent previous reaction zone, the benzene better effects if is fallen; Through comparative example 4 and 5 and embodiment 3 can know, to second reaction zone through adding catalyzer and/or add the conversion that raw material all more helps benzene, thereby can obtain the gasoline of lower benzene content; Simultaneously through embodiment 3 can be found out with Comparative Examples 3-4 contrast; In the reducing riser reactor, adopt active higher sieve catalyst, in higher reaction temperatures with than under the short residence time(SRT); Not only can obviously reduce benzene content in the gasoline, can also obtain comparatively ideal product and distribute.Embodiment 8, embodiment 9 can be found out C in raw material with embodiment 10 contrasts
9-C
12When aromaticity content was higher, the sieve catalyst that the sieve catalyst that mean pore size is bigger is littler than mean pore size more helped reducing benzene content in gasoline, but when the composite use of molecular sieve of different aperture sizes 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, this method comprises the gasoline that contains benzene contact at a plurality of reaction zones with catalytic cracking catalyst with alcohol successively, isolates the gasoline of benzene content reduction the mixture after contacting; Said a plurality of reaction zone comprises first reaction zone and the later reaction zone of first reaction zone; The contact temperature of any reaction zone that first reaction zone is later 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 any reaction zone contact that first reaction zone is later than residence time of low 30-300 ℃ of adjacent previous reaction zone, this reaction zone than adjacent previous reaction head of district 0.5-15s.
4. method according to claim 3, wherein, the temperature of any reaction zone contact that first reaction zone is later than residence time of low 50-250 ℃ of adjacent previous reaction zone, this reaction zone than adjacent previous reaction head of district 1-10s.
5. method according to claim 1 and 2, wherein, a plurality of reaction zones are provided by at least two combination of reactors of two kinds among fluidized-bed reactor, riser reactor, downstriker transfer limes reactor drum or three combinations or a kind of reactor drum at least.
6. method according to claim 5; Wherein, The number of reaction zone is 2, is provided by a riser reactor, along the flow direction of reactant flow; The conversion zone of said riser reactor comprises conversion zone and the bigger conversion zone of diameter that diameter is less, forms first reaction zone and second reaction zone respectively.
7. method according to claim 1 and 2; Wherein, This method also comprises in the later any one or more reaction zones of first reaction zone adds catalyzer, the reaction zone that make 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, the reaction zone that adds catalyzer than the agent weight of oil of adjacent last reaction zone than high 10-40%.
9. method according to claim 7, wherein, this method also comprises isolates reclaimable catalyst from post reaction mixture, and reclaimable catalyst is regenerated; At least a portion of said catalyzer is the catalyzer after regenerating.
10. method according to claim 1 and 2; Wherein, This method also comprises in the later any one or more reaction zones of first reaction zone adds gasoline and alcohol, make the reaction zone that adds gasoline and alcohol than the agent weight of oil of adjacent last reaction zone than low 10-50%.
11. method according to claim 10, wherein, the reaction zone that adds gasoline and alcohol than the agent weight of oil of adjacent last reaction zone than low 20-40%.
12. method according to claim 1, wherein, the condition of first reaction zone contact comprises that alcohol and the weight ratio that contains the gasoline of benzene are 0.01-1: 1.
13. method according to claim 12, wherein, the condition of first reaction zone contact comprises that alcohol and the weight ratio that contains the gasoline of benzene are 0.02-0.5: 1.
14. according to claim 1,2,12 or 13 described methods; Wherein, the condition of 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 that contains the gasoline of benzene: 1.
15. method 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 that contains the gasoline of benzene: 1.
16. method according to claim 1, wherein, alcohol is monohydroxy-alcohol and/or the polyvalent alcohol of 1-5 for carbonatoms.
17. method according to claim 16, wherein, alcohol is one or more in methyl alcohol, ethanol, propyl alcohol, terepthaloyl moietie, Ucar 35, USP Kosher, the tetramethylolmethane.
18. method according to claim 1, wherein, catalytic cracking catalyst contains zeolite and heat-resistant inorganic oxide, and said zeolite is mesopore and/or large pore zeolite.
19. method according to claim 1, wherein, the content that contains benzene in the gasoline of benzene is more than 0.5 weight %.
20. method according to claim 1 and 2, wherein, this method also comprises isolates reclaimable catalyst from post reaction mixture, and reclaimable catalyst is regenerated; At least a portion of said catalyzer is the catalyzer after regenerating.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2011
- 2011-03-17 CN CN201110064391.XA patent/CN102417829B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679680A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of catalysis conversion method of light fraction oil |
| CN109679680B (en) * | 2017-10-19 | 2021-01-08 | 中国石油化工股份有限公司 | Catalytic conversion method of light distillate oil |
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