CN1098084A - Produce the Nonextractive processes of high purity aromatics - Google Patents
Produce the Nonextractive processes of high purity aromatics Download PDFInfo
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- CN1098084A CN1098084A CN93107986A CN93107986A CN1098084A CN 1098084 A CN1098084 A CN 1098084A CN 93107986 A CN93107986 A CN 93107986A CN 93107986 A CN93107986 A CN 93107986A CN 1098084 A CN1098084 A CN 1098084A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/16—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
Abstract
Non-extracting novel method by hydrocarbon material flow production high purity and chemical pure aromatic hydrocarbons (as benzene, toluene, dimethylbenzene).The aroamtic hydrocarbon raw material logistics that contains narrow boiling point non-aromatic component is contacted with an acidic catalyst, and boiling point is in the non-aromatics impurity of aromatic hydrocarbons scope through being catalytically converted into boiling point other hydro carbons outside this aromatic hydrocarbons boiling point.The useful aromatic hydrocarbons distillation is separated.This paper also comprises the non-method for extracting that the dual catalytic agent is handled.
Description
The present invention relates to produce the novel method of aromatic hydrocarbons.More particularly, the present invention relates to a kind of catalysis process of the arene stream that is used for purifying, the boiling spread of contained non-aromatics impurity is identical with the temperature range of aromatic hydrocarbons in this arene stream.Most importantly, the present invention describes a kind of non-extracting catalysis process of production high purity aromatic hydrocarbons.
In the production process of petroleum chemicals, need to be substantially free of the high purity arene stream of non-aromatic compound.The aroamtic hydrocarbon raw material that petrochemical iy produced is suitable comprises benzene, toluene, and C
8Aromatic hydrocarbons.Usually, the by product during the petroleum naphtha catalytic reforming, made of this aromatic hydrocarbons and output with the form that is mixed with other component or as ethene.For example, along with the difference that process variable and raw material are formed, the product liquid of naphtha reforming output (being called reformate) contains the mixture of various hydrocarbon, and this mixture comprises such as benzene, and the aromatic hydrocarbons of toluene and dimethylbenzene and so on is referred to as BTX usually.
In case after aromatic substance separated with the non-compounds of group of narrow boiling point, just can reclaim highly purified benzene, toluene and C by distillation method
8Arene stream.Then this class logistics is used to make petrochemical intermediate such as ethylbenzene, vinylbenzene, hexanaphthene, cumene, phenol, p-Xylol, a dimethyl, o-Xylol and p-methylstyrene.
Since to the design requirements of tower or reflux ratio by distillation method from reformate or pyrolysis gasoline, reclaim the pure aromatics logistics industrial be not practicable.Therefore, rely on the partition method of boiling-point difference from reformate or pyrolysis gasoline, to separate narrow boiling point non-aromatics such as dimethylcyclopentane and hexanaphthene is impracticable with the purer aromatic product of generation.Though and can originally separate some non-aromatics with aryl at least based on the distillation method of boiling point, product still can contain one or more boiling points non-aromatics much at one.In practical field, when the boiling-point difference between various non-aromaticss and aromatic hydrocarbons during less than about 10, distillate will contain the mixture of aromatic hydrocarbons and non-aromatics.When being at least about 25 °F, boiling-point difference just can realize effective separation.
Use another kind of method, can use a kind of and non-aromatics to compare the high solvent of aromatic hydrocarbons relative affinity by means of extraction process and realize separating.The example that is generally used for the extraction process of industry is such as UOP ' SUDEX
TMAnd SULFOLANE
TMThe liquid of method and so on-liquid extracting or extractive distillation.
US3,808,284 and 3,812,197 specify together with catforming use the distillation and solvent extraction process.
Can use catalyzer from reformate, optionally to remove non-aromatics, US3 for example, 849,290 describe a kind of multistep processes that improves the petroleum naphtha gasoline concoction with the storing octane value.In the first step, raw material is reformed on nonacid platinum type catalyzer, produce a kind of reformate that contains aromatic hydrocarbons and paraffinic hydrocarbons.Make then reformate under the hydrocracking condition of gentleness with a kind of in the aperture zeolite contact and make the low-octane paraffinic hydrocarbons of high boiling point (as C
7+) optionally cracking.The effluent liquid of this hydrocracking step is contacted with a kind of small-bore catalyzer make the low-octane C of lower boiling
6The hydrocracking of-selective paraffin ground.These three steps, the processing sequence of three kinds of catalyzer generate a kind of high-octane rating product after preferentially removing the low octane rating hydrocarbon, but this degree of purity of production is not high enough concerning petroleum chemistry is used.
US4,795,550 describe and a kind ofly remove olefin impurity from arene stream, rather than the low-temperature catalyzed method of paraffinic hydrocarbons or naphthenic hydrocarbon, and the bromine index of this arene stream is between 50 and 2000.
US4,150,061 describe a kind of pyrolysis gasoline method of hydrodealkylation and transalkylation optionally that is used for making after the fractionation, and this pyrolysis gasoline comprises toluene, dimethylbenzene, ethylbenzene, C
7-C
10Paraffinic hydrocarbons, alkene and naphthenic hydrocarbon.This method is having few dimethylbenzene and the benzene of generation ethyl-benzene level under the situation of catalyzer.This catalyzer comprises a kind of tungsten/molybdenum component (WO
3-MoO
3) and a kind of acidic components (60%(weight) mordenite and 40%(weight) the catalytic activity aluminum oxide).Distill this product then with benzene and dimethylbenzene logistics that produces unknown purity and the toluene logistics that is used for recirculation.
US4,861,932 describe a kind of method of producing gasoline concoction with storing, wherein non-aromatics C
2-C
12Paraffin conversion becomes the mixture of high-octane rating aromatic hydrocarbons and alkylaromatic hydrocarbon, and method is that paraffinic hydrocarbons is contacted with a kind of precious metal/low acidity catalyzer.Make then effluent with a kind of based on containing of zeolite such as ZSM-5 a kind of metal contact such as an acidic catalyst of gallium (Ga), though the arenes selectivity height of known this Ga/ZSM-5 catalyzer, this degree of purity of production is not high enough concerning petroleum chemistry is used.
Still need innovative approach to develop catalysis process, this method is convenient on cost effectual ground production high purity arene stream such as BTX, and has minimally, and boiling point is in the non-aromatics impurity in the aromatic hydrocarbons scope.
Therefore an object of the present invention is to provide a kind of new catalysis process that obtains the high purity aromatic product.An other form of the present invention provides that a kind of be used for the non-aromatic component in the arene stream of boiling point in the aromatic hydrocarbons scope is changed into just can be easily with the isolating non-aromatics of aromatic hydrocarbons without extraction process in single catalytic step.
Have been found that now a kind of aroamtic hydrocarbon raw material that contains narrow boiling point non-aromatics can purify in single catalytic step, with production high purity aromatics Chemicals.More particularly, aroamtic hydrocarbon raw material is contacted with a kind of an acidic catalyst, draw a kind of product liquid, the boiling point of wherein contained non-aromatics impurity runs off this aromatic hydrocarbons boiling spread basically.Then can enough partition methods, high purity or chemical pure aromatic hydrocarbons are reclaimed in for example simple distillation from this product, and its expense is significantly less than industrial general extraction process at present.
In other embodiments, the enough a kind of method production of high-purity benzene energy, the non-aromatics impurity that wherein boiling spread is identical with benzene just can removing by selectivity succeeded by distillation by a kind of acidic zeolite catalyst under the elevated temperature condition.
In another embodiment of the invention, produce high-purity benzene, toluene or C with Nonextractive processes
8Aromatic hydrocarbons, this method are included in reformed naphtha logistics above a kind of non-acidic catalyst, make all or part of reformate reaction on a kind of an acidic catalyst, and reclaim the high purity aromatic product with distillation method.In another embodiment of the invention, this reformate of distillation contained toluene, or contains the cut of dimethylbenzene to obtain being rich in benzene before reformate reacted on an acidic catalyst.
Main purpose of the present invention is optionally to remove boiling point with Nonextractive processes from arene stream to be in benzene, and the non-aromatics impurity of toluene and dimethylbenzene (BTX) boiling range is with production high purity arene stream.This boiling range is usually directed to the temperature between about 140 and 350 (about 60 ℃ and 180 ℃).This class non-aromatics can be called narrow boiling point non-aromatics here.
This method generally includes by its selective reaction on an acidic catalyst and makes in the cracking of aromatic hydrocarbons scope ebullient non-aromatics impurity.Make narrow boiling point non-aromatics change into light paraffins and alkene that boiling point runs off the BTX scope basically.In some cases, can form more aromatic hydrocarbons by alkylation or aromizing light paraffins and alkene.
So-called " non-extracting " refers to and relies on solvent different and separate various hydro carbons according to boiling-point difference, by this class Nonextractive processes, the aromatic hydrocarbons purity that generates better is at least about 95%(weight), be more preferably weight) at least about 99.0%(, or even 99.5%(weight), preferably at least about 99.8%(weight).This class aromatic product here can be thought does not have non-aromatics impurity basically.
Catalyst acidity is absolutely necessary concerning non-extracting step of converting.As technically known, acidity of catalyst measure is the normal hexane cracking activity.For example, according to the α test, the α representative is compared a kind of relative normal hexane cracking activity of catalyzer with standard catalyst.This test illustrates more fully sees US3,354,078, and Journal of Catalysis.vol.6, p.522-529, (Ang.1965) with Journal of Catalysits vol.61, p.395(1980).
According to this test, as α＞about 10, perhaps be more preferably＞about 50 o'clock, catalyzer is a tart.The α value of strong acid catalyst＞about 100.Effectively an acidic catalyst is characterised in that this tart definition in the present invention.Particularly, effectively an acidic catalyst can be based on molecular sieve, such as ZSM-5, and beta-zeolite, X-zeolite, Y-zeolite, mordenite, ZSM-11, SSZ-23(sees US4,902,844), SSZ-25(sees US4,826,667) and SSZ-26(see US4,910,006).All these patents are all compiled in this for your guidance.
Since its performance of anti-blockage, the main component that middle pore size molecular sieve is to use the acidic catalyst agent method preferentially to select for use, and wherein this aroamtic hydrocarbon raw material is a gas phase.ZSM-5 is particularly preferred.Concerning aroamtic hydrocarbon raw material was the method for liquid phase, with the wide aperture molecular sieve, such as the X-zeolite, Y-zeolite, mordenite, beta-zeolite and SSZ-26 were that main an acidic catalyst is preferred.
This molecular sieve is preferably bonding with any varied inorganic oxide adhesive of knowing.Suitable binder comprises that molecular sieve can mix with it, disperses or with the mixed uniformly inorganic compositions of other method.Preferred oxide adhesive comprises aluminum oxide, silica, clay naturally occurring and that process routinely, for example wilkinite, kaolin, sepiolite, attapulgite and halloysite.
The selective conversion that contains non-aromatics in the many logistics of aromatic hydrocarbons can be carried out under gaseous state again in liquid state.And the occasion that liquid and gas are in equilibrium state under appropriate condition can provide proper raw material.
Usually, reaction conditions should reach the degree of impelling the non-aromatics preferred catalytic to transform.Concerning liquid phase process, process conditions such as pressure, should reach the liquid degree of considerable part raw material maintenance at least that makes.For example, pressure should be between about 150-1000psig.Preferred temperature is between about 500 °F-Yue 700 °F (260 ℃-371 ℃).Reinforced weight hourly space velocity can not wait from 0.1-100, and generally between 0.5 and 10.The existence of liquid phase is used for washing catalyst and keep its activity.
On the other hand, concerning gas phase process, usually, process conditions should reach and make raw material keep the gasiform degree.For example, temperature can be relatively higher than and pressure can be lower than liquid phase feed relatively.Suitable reaction temperature is more preferably between about 700 and 1100 (371 ℃-593 ℃) between about 600 and 1200 (204 ℃-1168 ℃), preferably between about 950 and 1100 (482 ℃-593 ℃).Pressure can be between normal pressure and 1000psig or is higher, and is preferred between 50psig-600psig.In addition, preferably gas-phase reaction should be carried out under the situation of hydrogen stopping up preventing having.The mol ratio of hydrogen and hydrocarbon feed is generally between 0.5 and 5.0.Following embodiment more clearly illustrates appropriate operational parameters.
Method of the present invention can be used for from various feedstock production high purity arene streams.Typical raw material comprises reformate, pyrolysis gasoline and their cut and mixture.These raw materials should contain the weight at least about 70%() aromatic hydrocarbons, better be at least about 80%(weight), be more preferably weight) at least about 90%(, so that the generation of light gas is reduced to minimum, and both increased the actual effect of the inventive method on cost, increased the suitability of non-method for extracting described here again.
In a preferred embodiment, the reformate that obtains by the reformed naphtha raw material is purified by the reaction on a kind of an acidic catalyst.This raw material can be a kind of light naphthar raw material, for example contains C
6And/or C
7The raw material that component is a lot of is reformed this raw material to produce a kind of product stream that contains aromatic hydrocarbons and narrow boiling point non-aromatics on any conventional reforming catalyst.Typical reforming process operational condition comprises: feed rate 0.1-10WHSV(weight hourly space velocity), pressure is between about 40psig and 100psig, and temperature is between about 800 °F and 1100 °F, and hydrogen: the mol ratio of raw material is between about 0.1-10.
Available a kind of non-acidic catalyst is with the reformed naphtha raw material and improve its aromaticity content.Therefore, the α value should＜10, preferably＜0.1.In fact the acidity of powerful catalyst is undesirable in aromatic hydrocarbons produces, because this will impel cracking, and this causes the reduction of arenes selectivity.For reducing acidity, catalyzer can contain a kind of basic metal and/or a kind of alkaline-earth metal.Be preferably in according to a conventional method synthetic when or afterwards basic metal or alkaline-earth metal are added in the catalyzer.In addition, better be at least 90%, be more preferably at least 95%, preferably 100% sour position is neutralized by introducing metal.
In addition, produce the catalyzer of aromatic hydrocarbons can aluminum oxide or molecular sieve be basic, such as L-zeolite that contains a kind of inorganic adhesive or low alumina zeolite, the preferred catalyst of reformation usefulness is included in beta-zeolite, ZSM-5, platiniferous catalyzer on the non-acid type formula of low alumina zeolite and L-zeolite.Other reforming catalyst of knowing generally contains a kind of catalytic metal such as platinum, and they are arranged on the natural and any superfluous position of artificial crystalline silico-aluminate.Metal promoters such as group VIII metal rhenium and indium also can be included, and also can be other promoter metal such as tin and germanium.
ZSM-5 and particularly be called its silica alumina ratio (SiO of low alumina zeolite sometimes
2: Al
2O
3) high ZSM-5, the example of its manufacturing process is seen: people such as Dwyer, US3,941,871(Mar.2,1976) and US4,441,991(Apr.10,1984); With people such as Derouane, european patent application 186,479(Feb.7,1986).All these patents are all compiled in this for your guidance.The preparation embodiment of the platinum catalyst on nonacid low alumina zeolite or the L-zeolite sees US4,830,732 and 5,073,250.
The low-sulfur raw material of aromatic hydrocarbons generation step can be said so attractive, so that avoid making reforming catalyst to poison.Under the situation of L-zeolite, better be＜50ppbw to be more preferably＜5ppbw to the sulphur content of the charging of reformer.
As a particular instance of a kind of like this aromatic hydrocarbons generation step of using the inventive method, can produce valuable C from less expensive hydrocarbon feed such as pyrolysis gasoline and alkane petroleum naphtha
6-C
8Aromatic hydrocarbons.Product is to contain ethylbenzene, benzene, the logistics of toluene and three kinds of xylene isomers.This aromatic hydrocarbons produces step this hydrocarbon feed is changed into very clean aromatic hydrocarbons mixture, yet this mixture also comprises narrow boiling point non-aromatics impurity.Method of the present invention is transformed this narrow boiling point non-aromatics impurity then and is produced a kind of energy through distilling the product that the high purity arene stream is provided.Therefore, this method is used two kinds of independent catalyzer: a kind of non-acidic catalyst is to produce aromatic hydrocarbons and a kind of an acidic catalyst aromatic hydrocarbons to purify and to be generated.
More particularly, this method can comprise that the hydrocarbon feed that makes a kind of cheapness is from process above the low alumina zeolite (alumina content is between about 200-2000ppm) of a kind of non-acidic catalyst such as platinum covering.This catalyzer is effective especially to the aromizing of charging, but as mentioned above, produces a kind of complex mixture that is difficult to the useful isolating non-aromatics of aromatic hydrocarbons that contains.Because the high benzene content (about 70-75%(weight) of product), this selectivity is being valuable aspect the production petroleum chemicals.
Secondly, as described in other form of the present invention, by a kind of an acidic catalyst narrow boiling point non-aromatic component is changed into lighter and heavier component this mixture of purifying, like this, this weight component just can for example be separated with aromatic hydrocarbons by distillation method easily.This impure distillate contains C
3-C
4And C
9+Hydro carbons, the latter can be used for further producing aromatic hydrocarbons through recirculation.This favourable combination of two kinds of different catalysts is enough to help the production of high purity aromatic hydrocarbons such as BTX.Following each embodiment specifies the method according to this embodiment.
Embodiment 1
Carry out aromizing to produce a kind of about 73%(weight that contains above making the platinum catalyst of a kind of lightweight reformate stream on a kind of nonacid low alumina zeolite (alumina content is lower than 2000ppm)) total BTX and about 22%(weight) other C
6+The product of hydro carbons.Making this contain a lot of product stream (relevant liquid feeding sees Table A) of aromatic hydrocarbons contacts with a kind of tart Ga/HZSM-5 catalyzer in 707 °F (375 ℃) under the situation that interpolation hydrogen is arranged, in another experiment, make liquid raw material not have at 842 °F (450 ℃) under the situation of hydrogen to contact with same an acidic catalyst.Other process conditions has regulation in Table A.
As specifying in the Table A, BTX is with respect to the C of liquid feed and product
6-C
8The percentage of total content is handled the back by the inventive method and account for 76.6%(weight in by charging in the liquid product stream that is rich in aromatic hydrocarbons separately) be increased to about 94%(weight) and about 98.9%(weight).Can from product stream, isolate high purity aromatic hydrocarbons easily by distillation method.
In another embodiment of the invention,, under the temperature condition that raises, can from the benzene streams, eliminate by the selective reaction of gas phase on a kind of acidic zeolite catalyst at the temperature range ebullient non-aromatics impurity identical with benzene.For example, C
5And heavy paraffin, cracking takes place in alkene and naphthenic hydrocarbon between 600 °F-1200 °F (316 ℃-649 ℃), form light paraffins and alkene.Alkene makes benzene and other alkylating aromatic hydrocarbon, stays a kind of aromatic fraction that is substantially free of narrow boiling point non-aromatics.When separating, it is heavy to access purity＞about 95%(
Amount) aromatic hydrocarbons.
Can make high-purity benzene by this method, this method comprises: reforming a kind of mainly is C
6Feed naphtha with generation＞70%(weight) aromatic hydrocarbons, in benzene and last running, separate lighting end by distillation, make benzene and last running reclaim the high-purity benzene cut through a kind of acid HZSM-5 and by distillation down at 800 °F-1100 °F (427 ℃-593 ℃).This method has been left out the liquid extracting or the extractive distillation process of needed costliness.
This embodiment of the present invention will further specify with embodiment 2 and 3.
Embodiment 2 and 3
Contain a lot (about 95%(weight) the isomeric hexane bodies of hexane having under the situation of hydrogen on the L-zeolite catalyst that non-acid platinum covers, to reform two kinds) feed naphtha flow.Collection contains about 75%(weight) the liquid reformate of benzene.The distillation reformate obtain 93%(weight respectively) and 99%(weight) the benzene cut.The charging of oxytropism step of converting is exactly these benzene cuts from each reformate.Mix the vaporization of these cuts and with hydrogen and to make the mixture peracidity HZSM-5 catalyzer of flowing through under the following conditions: pressure 150psig, 1000 of temperature (538 ℃), hydrogen and hydrocarbon mol ratio 4: 1, the WHSV of liquid feeding is 5.7.
Table B and C show that in the charging of oxytropism step of converting, all non-aromatics impurity all changes into C basically
1-C
4Paraffinic hydrocarbons and C
7+Aromatic hydrocarbons.Reclaim aromatic product by condensation method, light paraffins is then taken away by the hydrogen stream product.Ought to require further to distill aromatic fraction and be higher than 99.9%(weight to produce purity) benzene and be applicable to the C that gasoline is in harmonious proportion
7+Arene stream.
Table B
| Form wt% | Raw material | Product |
| C 1－C 4Paraffinic hydrocarbons 2,3 one dimethylbutane 2-methylpentane 3-methylpentane normal hexane C 6Alkene methyl cyclopentane 2; 4 one dimethyl pentane phenyl ring hexanes 2; 3 one dimethyl pentane 2-methyl hexane 3-methyl hexane normal heptane toluene ethylbenzene pair, meta-xylene ortho-xylene C9+ aromatic hydrocarbons | 0.014 0.047 0.070 0.159 0.022 0.234 0.069 93.041 0.007 0.072 0.045 0.008 0.048 4.441 0.086 0.201 0.120 1.323 | 0.841 0.004 91.129 5.978 1.014 0.426 0.152 0.456 |
Table C
| Form wt% | Raw material | Product |
| C 1－C 4Paraffinic hydrocarbons 2,3 one dimethylbutane 2-methylpentane 3-methylpentane normal hexane C 6Alkene methyl cyclopentane 2; 4 one dimethyl pentane phenyl ring hexanes 2; 3 one dimethyl pentane 2-methyl hexane 3-methyl hexane normal heptane toluene ethylbenzene pair, meta-xylene ortho-xylene C9+ aromatic hydrocarbons | 0.020 0.068 0.103 0.237 0.126 0.349 0.101 98.802 0.007 0.094 0.057 0.010 0.042 0.018 | 0.815 0.005 96.494 1.221 1.017 0.254 0.091 0.103 |
In another embodiment of the invention, can make high-purity benzene and dimethylbenzene by impure toluene logistics by an acidic catalyst such as beta-zeolite or the HZSM-5 that uses high cracking activity.Under the toluene disproportionation condition that raises, be up to about 10%(weight in the methylbenzene raw material stream) non-aromatics impurity be converted to lighting end, make purity in 99.5%-99.9%(weight) benzene, toluene and C
8Aromatic fraction, for example reclaiming by distillation becomes possibility.Like this, can make the toluene of reformate or pyrolysis gasoline streams partly flow to reactor, implement method of the present invention there, avoid extraction process, for example UDEX
TMInstall, and throughput is used for the production of benzene.Not pure toluene logistics in the liquid and gas can be reacted the last highly purified arene stream that generates on an acidic catalyst.
The present invention according to this embodiment is specified in embodiment 4 and 5.
Embodiment 4
Distillation has been sloughed the reformate of butane to obtain light and last running.Further the distillation heavy reformate is to 30% cut point.The overhead product of second distillation (containing about 92%(weight) toluene) vaporization, mix with hydrogen, flow through a tubular fixed bed reactor that acid ZSM-5 catalyzer is housed then.Be reflected at 1000 °F (538 ℃), carry out under 150psig and the 5.7 liquid toluene feed weight hourly space velocitys (WHSV).Hydrogen: the mol ratio of toluene is about 3: 1.
Under tabulate shown in the D raw material that streams obtained by the kapillary gas liquid chromatography and the analytical data of product after 9 hours.Flame ionization detector is housed and the polarity pillar of drip washing non-aromatics before aromatic hydrocarbons on the gas-chromatography.
Analytical data shows, makes benzene and dimethylbenzene with toluene disproportionation, and at the same time, the non-aromatics impurity that is in identical boiling range is eliminated basically by cracking and forms lighting end.Product can access highly purified aromatic hydrocarbons through distillation.
Embodiment 5
Toluene and C
7Mix with 92: 8 weight ratios, the liquid phase mixture of gained is reacted above entering current flow fixed bed reactor acidic beta-zeolite catalyst therein.Reaction conditions is: liquid feeding hourly space velocity (LHSV) 0.5,600 of temperature (316 ℃), pressure 600psig.Analyze raw material and product stream with the chromatographic instrument that flame ionization detector and nonpolar capillary column (by the boiling point elution fraction) are housed.Table E provides analytical results.
Table E
| Component | Retention time, minute | Area-percentage ratio | |
| Raw material | Product | ||
| Light fraction benzene non-aromatics toluene non-aromatics ethylbenzene pair, meta-xylene ortho-xylene C9+ aromatic hydrocarbons | 0.33-1.23 4.64 4.73-5.96 6.28 6.39-6.97 7.60 7.71 7.99 8.44-15.83 | 0.000 0.003 7.552 92.448 0.003 0.014 0.008 0.002 0.000 | 3.748 16.910 0.068 42.783 0.277 2.508 17.833 5.231 10.642 |
In addition, make toluene disproportionation to make benzene and dimethylbenzene, meanwhile, narrow boiling point non-aromatics is removed by cracking.The lighting end of some gained makes benzene alkylation form ethylbenzene, and valuable heavy arene then can be used as the gasoline blend component.Highly purified benzene is enough simply with the dimethylbenzene energy, distillation method is separated.
From embodiment as seen, the present invention described herein uses catalysis process with production high purity aromatic hydrocarbons.Method particularly described herein is for obtaining high purity aromatic hydrocarbons such as benzene and C
6Aromatic hydrocarbons provides effectively and direct approach.Do not rely on extraction process to eliminate narrow boiling point non-aromatics, a kind ofly be easy to the isolating non-aromatics of aromatic hydrocarbons according to boiling-point difference because can this non-aromatics preferentially be changed into by a kind of an acidic catalyst.
The versatility of this method can be by proving in conjunction with obtaining with production high purity arene stream such as reforming with other method.In addition, in conjunction with it seems that various hydrocarbon feeds can both use, to paraffinic feed, and charging can be liquid state and can be gaseous phase again from impure arene stream from these.In addition, method of the present invention considers that the processing of non-aromatics raw material can as described hereinly make it aromizing before acid purification step.Process conditions can be according to feedstock property, and the kind of catalyzer and economic condition are from selecting temperature (500-1200) and pressure (0-1000psig) scope widely.
The industry scope of application
The present invention is useful, because it can be from the aromatic hydrocarbons material flow production high-purity aromatic hydrocarbons of the non-aromatics impurity that contains the temperature range identical with aromatic hydrocarbons boiling. The aromatic hydrocarbons of purifying can be used as the petrochemistry raw material.
When the present invention has been described together with its specific embodiment, be to be understood that the present invention can further revise, and the application comprises any change of the present invention, purposes, perhaps adjust, generally speaking, follow principle of the present invention and comprise with this of the disclosure of invention and departing from, as being included in technical known or common way range, be subordinated to the present invention and as the principal character that can be applied to above regulation, and be subordinated to the row of the scope of the invention and the range of additional claim.
Claims (42)
1, made a kind of non-method for extracting of high purity aromatic hydrocarbons at least at least by the raw material that contains narrow boiling point paraffinic hydrocarbons of 70% (weight) aromatic hydrocarbons and 0.5% (weight) and naphthenic hydrocarbon non-aromatics, this method comprises following each step:
A) raw material is contacted under certain condition with a kind of an acidic catalyst, under this condition, narrow boiling point non-aromatics is changed into the hydro carbons of low and higher;
B) reclaim a kind of liquid aromatic product by distillation method, wherein this product contains at least 99% (weight) aromatic hydrocarbons.
2, according to the process of claim 1 wherein that this liquid state aromatic product contains 99.5%(weight at least) aromatic hydrocarbons.
3,, wherein should the liquid state aromatic product contain 99.8%(weight at least according to the method for claim 2) aromatic hydrocarbons.
4, according to the process of claim 1 wherein that raw material to the small part that is under the contact condition is liquid, the contact temperature is between about 500 °F (260 ℃) and about 700 °F (371 ℃).
5, according to the method for claim 4, wherein this an acidic catalyst is made up of a kind of wide aperture molecular sieve.
6, according to the method for claim 5, wherein this molecular sieve is by being selected from beta-zeolite, Y-zeolite, X-zeolite, a kind of large aperture zeolite composition of mordenite and SSZ-26.
7, according to the process of claim 1 wherein that the raw material that is under the contact condition is a gasiform, the contact temperature is between about 700 °F (371 ℃) and about 1100 °F (593 ℃).
8, according to the method for claim 7, wherein this an acidic catalyst is made up of pore size molecular sieve in a kind of.
9, according to the method for claim 8, wherein this molecular sieve is by being selected from ZSM-5, ZSM-11, a kind of middle aperture zeolite composition of SSZ-23 and SSZ-25.
10, according to the process of claim 1 wherein that this raw material contains toluene, this liquid state arene stream contains benzene and C
8Aromatic hydrocarbons.
11, according to the process of claim 1 wherein that this raw material is the product that a kind of light naphthar reacts on nonacid catalyst made from platonic.
12, according to the process of claim 1 wherein that this raw material is a kind of aromatic fraction of pyrolysis gasoline.
13, according to the process of claim 1 wherein that this raw material is a kind of aromatic fraction of reformate.
14, make paraffinic feed change into high-purity C
6-C
8A kind of non-method for extracting of aromatic hydrocarbons, this method comprises the following steps:
A) raw material is contacted to produce first effluent under certain condition with a kind of non-acidic catalyst, this first effluent comprises aromatic hydrocarbons and non-aromatics impurity, and the boiling point of this non-aromatics impurity is in the temperature range identical with this aromatic hydrocarbons;
B) first effluent is separated into the first non-aromatics cut and first aromatic fraction, this first aromatic fraction is by at least about 70%(weight) aromatic hydrocarbons forms;
C) this first aromatic fraction is contacted producing second effluent with a kind of an acidic catalyst, this second effluent is substantially free of boiling point and is in non-aromatics impurity with this aromatic hydrocarbons same temperature ranges stated;
D) second effluent is separated into second aromatic fraction and the second non-aromatics cut, the boiling point of contained non-aromatics runs off the boiling range of this second aromatic fraction basically in this second non-aromatics cut, and this second aromatic fraction is by 95%(weight at least) liquid C
6-C
8Aromatic hydrocarbons is formed.
15, according to the method for claim 14, wherein this second aromatic fraction is by 99%(weight at least) liquid C
6-C
8Aromatic hydrocarbons is formed.
16, according to the method for claim 14, wherein this second aromatic fraction is by 99.5%(weight at least) liquid C
6-C
8Aromatic hydrocarbons is formed.
17, according to the method for claim 14, wherein this second aromatic fraction is by 99.8%(weight at least) liquid C
6-C
8Aromatic hydrocarbons is formed.
18, according to the method for claim 14, wherein this non-acidic catalyst contains platinum.
19, according to the method for claim 14, wherein this non-acidic catalyst also comprises a kind of molecular sieve that is selected from low alumina zeolite and L-zeolite.
20, according to the method for claim 14, the raw material that wherein is under the contact condition is a gaseous state, and the contact temperature is between about 700 °F (371 ℃) and about 1100 °F (593 ℃).
21, according to the method for claim 20, wherein this an acidic catalyst is made up of pore size molecular sieve in a kind of.
22, according to the method for claim 21, wherein this molecular sieve is by being selected from ZSM-5, ZSM-11, a kind of middle aperture zeolite composition of SSZ-23 and SSZ-25.
23, according to the method for claim 14, raw material to the small part that wherein is under the contact condition is liquid, and the contact temperature is between about 500 °F (260 ℃) and about 700 °F (371 ℃).
24, according to the method for claim 23, wherein this an acidic catalyst is made up of a kind of wide aperture molecular sieve.
25, according to the method for claim 24, wherein this molecular sieve is by being selected from beta-zeolite, Y-zeolite, X-zeolite, a kind of large aperture zeolite composition of mordenite and SSZ-26.
26, according to the method for claim 20, wherein this an acidic catalyst also comprises a kind of metal, and this metal is selected from gallium and zinc.
27, according to the method for claim 14, wherein this raw material is a kind of low-sulfur paraffinic hydrocarbons streams.
28, according to the method for claim 14, wherein this raw material is a kind of paraffinic hydrocarbons petroleum naphtha.
29, according to the method for claim 14, wherein this raw material is a kind of pyrolysis gasoline.
30, according to the method for claim 14, this C wherein
6-C
8Aromatic hydrocarbons is by ethylbenzene, benzene, and toluene and dimethylbenzene are formed.
31, according to the method for claim 14, this C wherein
6-C
8Aromatic hydrocarbons reclaims by distillation method.
32, by C
6-C
8Paraffinic feed is made a kind of non-method for extracting of high purity aromatic hydrocarbons, and this method comprises:
A) on a kind of non-acidic catalyst, reform this raw material so that a kind of 70%(weight at least that contains to be provided) aromatic hydrocarbons and 0.5%(weight at least) reformate of narrow boiling point paraffinic hydrocarbons and naphthenic hydrocarbon non-aromatics, wherein the condition of reorganization comprises WHSV0.1-10, pressure is between about 40psig and 100psig, temperature is between about 800 and 1100 (427 ℃-593 ℃), and hydrogen: material molar ratio is between about 0.1-10;
B) reformate is contacted with a kind of an acidic catalyst;
C) reclaim a kind of liquid aromatic product by distillation method, this product is by 99%(weight at least) aromatic hydrocarbons forms.
33, according to the method for claim 32, the purity of this liquid phenenyl＞about 99.5%(weight wherein).
34, according to the method for claim 33, the purity of this liquid phenenyl＞about 99.8%(weight wherein).
35, according to the method for claim 32, wherein this raw material is a kind of low-sulfur petroleum naphtha streams.
36, according to the method for claim 32, wherein this reforming catalyst is made up of the L-zeolite.
37, according to the method for claim 35, this first aromatic fraction to the small part that wherein is under the contact condition is liquid, and the contact temperature is between about 500 °F (260 ℃) and about 700 °F (371 ℃).
38, according to the method for claim 32, wherein this an acidic catalyst is made up of pore size molecular sieve in a kind of.
39, according to the method for claim 32, wherein this molecular sieve is by being selected from ZSM-5, ZSM-11, a kind of middle aperture zeolite composition of SSZ-23 and SSZ-25.
40, according to the method for claim 35, this first aromatic fraction that wherein is under the contact condition is a gaseous state, and the contact temperature is between about 700 °F (371 ℃) and about 1100 °F (593 ℃).
41, according to the method for claim 40, wherein this an acidic catalyst is made up of a kind of wide aperture molecular sieve.
42, according to the method for claim 41, wherein this molecular sieve is by being selected from beta-zeolite, Y-zeolite, X-zeolite, a kind of large aperture zeolite composition of mordenite and SSZ-26.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU45390/93A AU4539093A (en) | 1992-06-18 | 1993-06-16 | Nonextractive processes for producing high purity aromatics |
| PCT/US1993/005814 WO1994000409A1 (en) | 1992-06-18 | 1993-06-16 | Nonextractive processes for producing high purity aromatics |
| DE4393010A DE4393010C1 (en) | 1992-06-18 | 1993-06-16 | Non-extracting process for the production of high purity aromatics |
| GB9416348A GB2279661B (en) | 1992-06-18 | 1993-06-16 | Nonextractive processes for producing high purity aromatics |
| CA002139785A CA2139785A1 (en) | 1992-06-18 | 1993-06-16 | Nonextractive processes for producing high purity aromatics |
| ZA934391A ZA934391B (en) | 1992-06-18 | 1993-06-18 | Nonextractive processes for producing high purity aromatics. |
| CN93107986A CN1098084A (en) | 1992-06-18 | 1993-07-24 | Produce the Nonextractive processes of high purity aromatics |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US90085792A | 1992-06-18 | 1992-06-18 | |
| CN93107986A CN1098084A (en) | 1992-06-18 | 1993-07-24 | Produce the Nonextractive processes of high purity aromatics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1098084A true CN1098084A (en) | 1995-02-01 |
Family
ID=36829905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93107986A Pending CN1098084A (en) | 1992-06-18 | 1993-07-24 | Produce the Nonextractive processes of high purity aromatics |
Country Status (7)
| Country | Link |
|---|---|
| CN (1) | CN1098084A (en) |
| AU (1) | AU4539093A (en) |
| CA (1) | CA2139785A1 (en) |
| DE (1) | DE4393010C1 (en) |
| GB (1) | GB2279661B (en) |
| WO (1) | WO1994000409A1 (en) |
| ZA (1) | ZA934391B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104574B (en) * | 2006-06-21 | 2012-08-22 | 环球油品公司 | Energy-efficient process for para-xylene production |
| CN106660896A (en) * | 2014-06-26 | 2017-05-10 | Sabic环球技术有限责任公司 | Process for producing purified aromatic hydrocarbons from mixed hydrocarbon feedstream |
| CN106660900A (en) * | 2014-06-13 | 2017-05-10 | Sabic环球技术有限责任公司 | Process for producing benzene from a c5-c12 hydrocarbon mixture |
| CN107955644A (en) * | 2016-10-18 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of efficient aromatization method of non-aromatic lighter hydrocarbons |
| CN109689842A (en) * | 2016-09-12 | 2019-04-26 | 沙特基础工业全球技术有限公司 | Method for hydrogen cracking |
| US10654767B2 (en) | 2014-06-26 | 2020-05-19 | Sabic Global Technologies B.V. | Process for producing alkylated aromatic hydrocarbons from a mixed hydrocarbon feedstream |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7731839B2 (en) | 2005-05-27 | 2010-06-08 | Exxonmobil Chemical Patents Inc. | Process for reducing bromine index of hydrocarbon feedstocks |
| US7744750B2 (en) | 2005-11-17 | 2010-06-29 | Exxonmobil Chemical Patents Inc. | Process for reducing Bromine Index of hydrocarbon feedstocks |
| US8057664B2 (en) | 2005-11-17 | 2011-11-15 | Exxonmobil Chemical Patents, Inc. | Process for reducing bromine index of hydrocarbon feedstocks |
| US7517824B2 (en) | 2005-12-06 | 2009-04-14 | Exxonmobil Chemical Company | Process for steam stripping hydrocarbons from a bromine index reduction catalyst |
| US8216450B2 (en) | 2009-04-22 | 2012-07-10 | Exxonmobil Chemical Patents Inc. | Removal of bromine index contaminants from aromatic streams |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3849290A (en) * | 1972-08-02 | 1974-11-19 | Mobil Oil Corp | Upgrading of reformates by catalyst compositions selective for cracking low and high boiling paraffin components |
| US3812197A (en) * | 1972-08-25 | 1974-05-21 | Texaco Inc | Method for disproportionating hydrocarbons |
| US3808284A (en) * | 1972-09-11 | 1974-04-30 | Texaco Inc | Process for disproportionating hydrocarbons |
| US4150061A (en) * | 1977-11-08 | 1979-04-17 | Standard Oil Company (Indiana) | Process for converting pyrolysis gasoline to benzene and ethylbenzene-lean xylenes |
| US4441991A (en) * | 1981-04-21 | 1984-04-10 | Mobil Oil Corporation | Catalytic dewaxing of oils containing ammonia over highly siliceous porous crystalline materials of the zeolite ZSM-5 type |
| US4861932A (en) * | 1987-12-31 | 1989-08-29 | Mobil Oil Corp. | Aromatization process |
| US5037529A (en) * | 1989-12-29 | 1991-08-06 | Mobil Oil Corp. | Integrated low pressure aromatization process |
-
1993
- 1993-06-16 WO PCT/US1993/005814 patent/WO1994000409A1/en active Application Filing
- 1993-06-16 DE DE4393010A patent/DE4393010C1/en not_active Expired - Fee Related
- 1993-06-16 AU AU45390/93A patent/AU4539093A/en not_active Abandoned
- 1993-06-16 CA CA002139785A patent/CA2139785A1/en not_active Abandoned
- 1993-06-16 GB GB9416348A patent/GB2279661B/en not_active Expired - Fee Related
- 1993-06-18 ZA ZA934391A patent/ZA934391B/en unknown
- 1993-07-24 CN CN93107986A patent/CN1098084A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104574B (en) * | 2006-06-21 | 2012-08-22 | 环球油品公司 | Energy-efficient process for para-xylene production |
| CN106660900A (en) * | 2014-06-13 | 2017-05-10 | Sabic环球技术有限责任公司 | Process for producing benzene from a c5-c12 hydrocarbon mixture |
| CN113214037A (en) * | 2014-06-13 | 2021-08-06 | Sabic环球技术有限责任公司 | From C5-C12Process for producing benzene from hydrocarbon mixture |
| CN106660896A (en) * | 2014-06-26 | 2017-05-10 | Sabic环球技术有限责任公司 | Process for producing purified aromatic hydrocarbons from mixed hydrocarbon feedstream |
| US10654767B2 (en) | 2014-06-26 | 2020-05-19 | Sabic Global Technologies B.V. | Process for producing alkylated aromatic hydrocarbons from a mixed hydrocarbon feedstream |
| CN114644542A (en) * | 2014-06-26 | 2022-06-21 | Sabic环球技术有限责任公司 | Process for producing purified aromatic hydrocarbons from mixed hydrocarbon feedstream |
| CN109689842A (en) * | 2016-09-12 | 2019-04-26 | 沙特基础工业全球技术有限公司 | Method for hydrogen cracking |
| CN109689842B (en) * | 2016-09-12 | 2021-01-29 | 沙特基础工业全球技术有限公司 | Hydrocracking process |
| CN107955644A (en) * | 2016-10-18 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of efficient aromatization method of non-aromatic lighter hydrocarbons |
| CN107955644B (en) * | 2016-10-18 | 2020-07-14 | 中国石油化工股份有限公司 | Efficient aromatization method of non-aromatic light hydrocarbon |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2279661A (en) | 1995-01-11 |
| GB9416348D0 (en) | 1994-10-05 |
| CA2139785A1 (en) | 1994-01-06 |
| ZA934391B (en) | 1994-01-17 |
| DE4393010C1 (en) | 1997-05-07 |
| GB2279661B (en) | 1996-05-01 |
| WO1994000409A1 (en) | 1994-01-06 |
| AU4539093A (en) | 1994-01-24 |
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