CN101734986A - Method for hydrogenation pyrolysis of prolific benzene and xylene by using pyrolysis gasoline - Google Patents
Method for hydrogenation pyrolysis of prolific benzene and xylene by using pyrolysis gasoline Download PDFInfo
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Abstract
The invention relates to a method for hydrogenation pyrolysis of prolific benzene and xylene by using pyrolysis gasoline. The method mainly solves the problems that only BTX (B is benzene, T is toluene and X is xylene) arene is separated in the traditional process of the pyrolysis gasoline, and the light arene output contains a great amount of toluene with lower utilization value with the separated heavy arene. In the invention, alkyl transfer reaction is carried out among the pyrolysis gasoline material of C7+, the heavy arene hydrogenation and the light arene are in the presence of catalyst, and isomerization reaction is carried out on the light arene into the component rick in BTX light arene; and the liquid-phase is separated into benzene, toluene, xylene and C9+ distillate according to different boiling points, wherein the toluene and the C9+ distillate can be returned for further processing as the feedstock and the light alkane can be separated from gas-phase output, thereby favorably solving the technical problem. The method can be used for the industrial production of light arene.
Description
Technical field
The present invention relates to a kind of method of utilizing pyrolysis gasoline hydrogenation cracking fecund benzene and dimethylbenzene.
Background technology
Industrial generally is reforming process reformate of making and the pyrolysis gasoline that is obtained by the naphtha cracking to be carried out solvent extraction separate BTX aromatic hydrocarbons and non-aromatics, this process is according to aromatic hydrocarbons, the polarity difference of non-aromatics in using solvent, reaches the purpose of separate targets aromatic hydrocarbons.Though solvent extraction BTX can obtain the BTX aromatic hydrocarbons of higher degree, but need the complicated solvent extraction device of a cover, and extraction solvent needs to replenish into continuously in the extraction procedure process, the solvent extraction method is favourable from obtaining highly purified aromatic hydrocarbon mixing, but from the extra solvent extraction equipment of needs with to drop into solvent continuously at equipment needs in service be disadvantageous, so the solvent extraction process has occupied the very big ratio of producing BTX aromatic hydrocarbons cost.Contain a large amount of toluene from the lightweight aromatic product in the product, lower with heavy arene and non-aromatic utility value after separating, the value of benzene and dimethylbenzene is higher by contrast.
U.S. Patent No. 3,729,409 propose to change into low-carbon alkanes by the hydrocracking reaction with aromatic hydrocarbons blended non-aromatic hydrocarbon in the presence of catalyzer, can isolate aromatic hydrocarbons by the vapour-liquid separator from non-aromatics.In addition, U.S. Patent No. 3,849,290 and 3,950,241 have also proposed a kind ofly changing into gaseous component to increase aromaticity content in liquid composition to prepare the method for high-quality ethereal oil component through hydrocracking reaction by making with aromatic hydrocarbons blended straight chain hydrocarbon component in the presence of the ZSM-5 type zeolite.U.S. Patent No. 5,865,986 and No.6,001,241 has further disclosed a kind of naphtha cut upgrade method, by catalyst based at partial reaction device mesolite, to increase the output of aromatic hydrocarbons.Korea S SK patent CN1217892C can be prepared into liquefied petroleum gas (LPG) and light aromatics with upgradings such as reformate and pyrolysis gasolines by similar approach.
An acidic catalyst need overcome the rapid deactivation problem that the coking carbon distribution causes, can have highly hydrogenated active metal group by load and assign to be suppressed.The hydrogenation activity of metal center is crossed and can be caused that by force another side reaction aromatic ring is saturated, United States Patent (USP) 5,865, and 986 propose to use sulphur compound to control metal active.In addition, in U.S. Patent No. 6,001, in 241, control degree of hydrogenation with lead or bismuth.
Summary of the invention
Technical problem to be solved by this invention is that pyrolysis gasoline conventional solvent extracting sepn process existence only simply separates BTX (B is that benzene, T are that toluene, X are dimethylbenzene) aromatic hydrocarbons, a large amount of toluene and heavy arene and non-aromatic are arranged in the light aromatics product, the problem that its utility value is lower provides a kind of new method of utilizing pyrolysis gasoline hydrogenation cracking fecund benzene and dimethylbenzene.This method has hydrocarbon raw material and separates simply, avoids the solvent extraction process, and product added value height can effectively utilize the advantage of cracking by-product and low value aromatic hydrocarbons.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of utilizing pyrolysis gasoline hydrogenation cracking fecund benzene and dimethylbenzene may further comprise the steps successively:
A) with hydrogen and C
7 +For raw material feeds at least one reaction zone, C wherein
7 +Be carbon seven and above hydrocarbon thereof;
B) in reaction zone, in the presence of catalyzer and under the effective reaction conditions, heavy arene generation hydro-dealkylation in the raw material, with light aromatics generation transalkylation reaction, light aromatics isomerization reaction and non-aromatics hydrocracking reaction, making feedstock conversion is to be rich in the light aromatics of benzene, toluene and dimethylbenzene and the stream I of light paraffins component;
C) stream I is separated and distillation by vapour-liquid, reclaims light aromatics and light paraffins respectively, and the heavy ends circulation is returned and entered the reaction zone utilization;
Wherein used catalyzer comprises following component in parts by weight: a) at least a in 0.01～0.8 part of metal that is selected from Pt or Pd or the oxide compound; B) 99.2～99.99 parts be selected from and have at least a in the 10 yuan of rings or the Zeolite support in 12 yuan of annular distance cracks.
In the technique scheme, select in the catalyzer that at least a consumption is 0.01～0.5 part in the parts by weight preferable range in the metal of Pt or Pd or the oxide compound for use.For the hydrogenation activity catalyzer preferred version of regulating precious metal is also to contain at least a in the metal that is selected from Cu, Sn, Pb, Zn or Fe or the oxide compound in the catalyzer to introduce as assistant metal, its consumption with parts by weight count＞0～1 part.The Zeolite support that Zeolite support is selected the binder free zeolite for use or used binding agent to be shaped, zeolite type is selected from mordenite, Y zeolite, β zeolite, ZSM-5 zeolite or ZSM-11 zeolite, is preferably mordenite or ZSM-5 zeolite.The silica/alumina mole ratio scope of zeolite is 10～200, and preferable range is 20～100.Zeolite is synthetic with the preparation of sodium type, carry out ion-exchange with acid solutions such as ammonium salt solution or hydrochloric acid then, carry out roasting after the exchange and be converted into h-type zeolite, introduce at least a metal or the oxide compound of Pt or Pd then by ion-exchange or dipping method, use Palladous chloride, Palladous nitrate, ammonium palladic chloride, ammonium palladous chloride, platinum nitrate, Platinic chloride, ammonium chloroplatinate, ammonium chloroplatinite, dichloro four ammoniums close at least a aqueous solution of platinum as precursor.The binder free h-type zeolite is introduced after Pt or the Pd, carries out drying under less than 200 ℃, at 300～600 ℃ dried catalyzer is calcined then.
Feed the C of reaction zone in the technique scheme in the step a)
7 +The weight space velocity scope of raw material is 0.5～10 hour
-1, be preferably 1～4 hour
-1, hydrogen/C
7 +Raw material is 0.5～10: 1 with the molar ratio computing scope, and preferable range is 2: 1～8: 1; Temperature of reaction preferable range in the described step b) is 250～600 ℃, and preferable range is 300～500 ℃, and the reaction pressure scope is 0.5～5.0MPa, and preferable range is 2.0～4.0MPa; Described C
7 +The raw material preferred version is selected from C
7 +Pyrolysis gasoline raw material or C
7 +Gasoline stocks and toluene, reformation C
7 +The mixture of aromatic hydrocarbons, catalytic cracking cut; Boiling point according to compound in the described step c) is separated into benzene,toluene,xylene and C respectively
9 +Cut, be specially that stream I is separated by vapour-liquid and distillation feeds the vapour-liquid separator, with obtain to comprise first overhead stream of hydrogen, methane, ethane and LPG component and comprise aromatic component and first tower base stream of small quantity of hydrogen and non-aromatic component to reclaim liquefied petroleum gas (LPG) from first overhead fraction be LPG; First tower base stream is fed in the distillation tower, with second tower base stream that obtains to comprise second overhead stream of remaining hydrogen and non-aromatic component and comprise aromatic component; From second overhead stream, reclaim liquefied petroleum gas (LPG), and from described second tower base stream, reclaim aromatic component, gained toluene and C
9 +Cut returns as charging and proceeds to handle, wherein C
9 +Be carbon nine and above hydrocarbon thereof.
The catalyzer that the present invention relates to utilize the method for pyrolysis gasoline hydrogenation cracking fecund benzene and dimethylbenzene and be used for this method.For benzene and the dimethylbenzene aromatic hydrocarbons that obtains high yield, require the content of benzene less relatively in the raw material, and toluene and heavy arene content are higher relatively.The hydrocracking reaction of non-aromatic component, the hydro-dealkylation of aromatic component, transalkylation and isomerization reaction are carried out in the presence of catalyzer of the present invention simultaneously.By described reaction, can obtain benzene, toluene and dimethylbenzene (BTX), they are important petrochemical complex organic raw material, wherein mainly increase production benzene and dimethylbenzene, wherein gained toluene and C
9 +Cut can return as charging and proceed to handle the output that further transforms raising benzene and dimethylbenzene.It is most important that hydrocracking is reflected in the described reaction, because the liquid phase non-aromatics in the hydrocarbon raw material is converted into the light paraffins that is rich in LPG, so the present invention do not need solvent extraction, finishes aromatics separation from the products therefrom of above-mentioned reaction.In addition, hydro-dealkylation reaction transalkylation and isomerization reaction can improve the quality the aromatic component in the hydrocarbon raw material.
According to the present invention, described reaction is undertaken by the zeolite based catalysts that use has than the strongly-acid center.The acid carrier of catalyzer is based on zeolite, and described zeolite is selected from zeolite with 10 yuan of rings and 12 yuan of annular distance cracks and their mixture.
In above-mentioned hydrocracking and dealkylation, can produce for example alkene such as ethene, propylene intermediate, promptly hydrogenation is saturated to prevent that olefinic polymerization from impelling coke to form to cause catalyst deactivation or causing the character variation of aromatic component in the product with light aromatics generation alkylated reaction.Therefore, have the hydrogenating function that acid sites is complementary in the catalyzer, should contain the metallic element of group VIII in the periodic table of elements with hydrogenation.
Metal component Pt or Pd all have good hydrogenation effect, the problem that should consider in Preparation of Catalyst that acidity of catalyst center and hydrogenation metal center are complementary and raw material is adapted to.Acid sites can be mediated by the silica/alumina mole ratio of adjustment zeolite molecular sieve or by modification, and the hydrogenation activity of metal center can be adjusted by the dispersity of content of metal, loaded metal.May contain the raw material that suppresses metal hydrogenation performance component for raw material is comparatively complicated, pyrolysis gasoline raw material such as sulfur compound, can consider two kinds of metal composite of Pt, Pd together, thereby this all can have good sulfur resistance than independent any one metal of use Pt, Pd and keeps good hydrogenation performance.Two kinds of metal composite of Pt, Pd can produce electro ultrafiltration or chemical action mutually, rather than separately exist in the catalyzer, thereby good hydrogenation and sulfur resistance is provided.
Catalyzer of the present invention adopts Zeolite support or the binder free Zeolite support that contains binding agent, wherein adopt the binder free zeolite as acidic components, it is big to have sour density, the characteristics that the aperture is unobstructed, metal hydrogenation component has the characteristics of hydrogenation moderate performance, in the reaction of pyrolysis gasoline hydrogenation cracking fecund benzene and dimethylbenzene, have good activity and stable, increased production the benzene and the dimethylbenzene of high added value to a great extent.
The efficient dual-function catalyst that the invention provides a kind of Zeolite support carried noble metal is used for the method for pyrolysis gasoline hydrogenation cracking fecund benzene and dimethylbenzene, generate the BTX light aromatics of high added value by the heavy arene in this process raw material, and benzene and dimethylbenzene have mainly been increased production in the mutual conversion between the aromatic hydrocarbons, and light paraffins such as by-product partial liquefaction petroleum gas, can be used as the high-quality cracking stock, product is because the boiling point difference can obtain highly purified aromatic product and by product liquefied petroleum gas (LPG) by distillation more greatly, thereby avoided the solvent extraction process, obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1～4]
Adhesiveless ZSM-5 zeolite (SiO
2/ Al
2O
3Mol ratio is 60) with reference to Chinese patent CN1915820 preparation, carry out ion-exchange with ammonium nitrate solution then, carry out roasting after the exchange and be converted into h-type zeolite.The Pt of 0.04 part of dip loading parts by weight meter and 0.10 part Sn on Hydrogen adhesiveless ZSM-5 zeolite 450 ℃ of calcinings 4 hours down, obtain catalyzer a.
Use a catalyzer of reduction activation to react examination, catalyzer in fixed-bed reactor at hydrogen pressure 3.0MPa, H
2/ oil volume is than 400～600,350～380 ℃ of reaction temperature ins, weight hourly space velocity WHSV=2.0～4.0 hour
-1Situation under check and rate, reaction result is listed in table 1:
Table 1 catalyzer a reacts liquid product
Wherein NA is a non-aromatics, C
10 +Be carbon ten and above hydrocarbon thereof, E is an ethylbenzene.
Benzene and toluene level are higher in embodiment 1 raw material, and handling back toluene by hydrocracking has bigger increment, and benzene and dimethylbenzene only have a small amount of growth; Along with benzene content in the raw material reduces, the raising of toluene level is handled back benzene and toluene and is all increased raising thereupon among the embodiment 2～4, and the increment of toluene reduces, and the raw material toluene level is the highest among the embodiment 4, handles back toluene and does not increase counter falling.This is because the conversion between the aromatic hydrocarbons is subjected to the restriction of molecular balance in this reaction, use the pyrolysis gasoline that contains more benzene handle since in the raw material content of benzene very up to 30～40%, therefore less through the increment of handling benzene afterwards.Adopt C
7 +The pyrolysis gasoline raw material wherein content of benzene is less, therefore the increment of handling back benzene is bigger, along with content of toluene in the raw material increases, the increment of benzene and dimethylbenzene is more obvious, and the conversion that self also can take place to a certain degree after toluene is increased to a certain degree in the raw material generates benzene and dimethylbenzene.
[embodiment 5～8]
Respectively at Hydrogen adhesiveless ZSM-5 zeolite (SiO
2/ Al
2O
3Mol ratio is 90) go up the Pt of 0.01 part of load weight umber meter and 0.03 part Pb, the Zn of 0.05 part Pt and 0.08 part, the Pd of 0.08 part Pt and 0.17 part, 0.50 part Pd, 450 ℃ down calcining obtained catalyzer b, c, d and e in 4 hours.
[embodiment 9～10]
Take by weighing the white carbon black of 180 grams, 60 gram sodium type mordenite ((SiO
2/ Al
2O
3Mol ratio is 30), 10 the gram sodium hydroxide, 50 the gram siliceous aluminum oxide powders (contain Al
2O
3Mass percent is 43%) and 10 gram sesbania powder, add 550 gram silicon sol (weight percent is 40%) again and mix the pinching bar and become cylindric shape, then in air atmosphere in 550 ℃ of roastings four hours.Be respectively that 4% tetraethyl ammonium hydroxide (TEAOH) solution mixes and places crystallizing kettle to carry out hydrothermal treatment consists 5 days under 160 ℃ with cylindric presoma and the 80 gram mass percentage concentrations of the above-mentioned preparation of 40 grams, product prepares binder free mordenite in 550 ℃ of roastings with distilled water wash oven dry back in air atmosphere, prepare Hydrogen binder free mordenite through ion-exchange.
The Pt of 0.06 part of load weight umber meter and 0.08 part Cu on Hydrogen binder free mordenite respectively, the Fe of 0.04 part Pt and 0.10 part, 450 ℃ down calcining obtained catalyzer f and g in 4 hours.
[embodiment 11～12]
ZSM-5 zeolite (SiO
2/ Al
2O
3Mol ratio is 60) prepare with reference to Chinese patent CN1915819, carry out ion-exchange with ammonium nitrate solution then, carry out roasting after the exchange and be converted into h-type zeolite, with aluminum oxide powder and silicon sol the h-type zeolite zeolite is carried out moulding respectively again, make salic in 35 parts of parts by weight Zeolite support and contain the Zeolite support of silicon-dioxide in 29 parts of parts by weight.The Pt of 0.04 part of load weight umber meter and 0.04 part Pd on above-mentioned two kinds of carriers respectively, 450 ℃ down calcining obtained catalyzer h and i in 4 hours.
Use the b～i catalyzer of reduction activation to react examination, reaction raw materials and reaction conditions are with reference to embodiment 3, and reaction result is listed in table 2:
Table 2 catalyzer b～g reacts liquid product (weight %)
| Catalyzer | ??b | ??c | ??d | ??e | ??f | ??g | ??h | ??i |
| ??B | ??19.54 | ??20.23 | ??21.01 | ??20.45 | ??21.50 | ??20.03 | ??17.06 | ??14.91 |
| ??T | ??33.87 | ??32.87 | ??31.98 | ??32.53 | ??31.03 | ??32.13 | ??31.25 | ??30.32 |
| ??E | ??0.6 | ??0.39 | ??0.36 | ??0.39 | ??0.32 | ??0.42 | ??1.97 | ??3.21 |
| ??X | ??16.99 | ??17.66 | ??18.12 | ??17.82 | ??18.32 | ??17.77 | ??13.53 | ??13.17 |
| ??C 6～C 8NA | ??0.25 | ??0.23 | ??0.22 | ??0.24 | ??0.25 | ??0.28 | ??0.53 | ??0.62 |
| ??C 9 | ??4.54 | ??3.99 | ??3.67 | ??3.92 | ??3.56 | ??3.98 | ??9.67 | ??12.38 |
| ??C 10 + | ??6.02 | ??5.03 | ??4.61 | ??4.99 | ??4.55 | ??4.81 | ??10.21 | ??11.57 |
| Volume increase (B+X) | ??22.71 | ??24.07 | ??25.31 | ??24.45 | ??26 | ??23.98 | ??16.77 | ??14.26 |
| Volume increase (B+T+X) | ??26.45 | ??26.81 | ??27.16 | ??26.85 | ??26.9 | ??25.98 | ??17.89 | ??14.45 |
| ??C 9Transformation efficiency % | ??84.90 | ??86.73 | ??87.80 | ??86.96 | ??88.16 | ??86.76 | ??67.84 | ??58.83 |
Wherein NA is a non-aromatics, C
10 +Be carbon ten and above hydrocarbon thereof.
By the data of table 1～2 as can be seen, (h i) compares, and obviously has better hydro-dealkylation activity and lytic activity based on the catalyzer of binder free zeolite, is specially C with the zeolite based catalysts that contains binding agent
9Transformation efficiency is higher, can increase production more benzene and dimethylbenzene.
Above-mentioned product is separated into benzene,toluene,xylene and C respectively according to the boiling point of compound
9 +Cut, be specially that stream I is separated by vapour-liquid and distillation feeds the vapour-liquid separator, to obtain comprising first overhead stream of hydrogen, methane, ethane and LPG component and to comprise aromatic component and first tower base stream of small quantity of hydrogen and non-aromatic component reclaims liquefied petroleum gas (LPG) from first overhead fraction; First tower base stream is fed in the distillation tower, with second tower base stream that obtains to comprise second overhead stream of remaining hydrogen and non-aromatic component and comprise aromatic component; From second overhead stream, reclaim liquefied petroleum gas (LPG), and from described second tower base stream, reclaim aromatic component, according to aromatic hydrocarbons market situation decision gained toluene and C
9 +Whether cut returns as charging is proceeded to handle.
Claims (10)
1. method of utilizing pyrolysis gasoline hydrogenation cracking fecund benzene and dimethylbenzene may further comprise the steps successively:
A) with hydrogen and C
7 +For raw material feeds at least one reaction zone, C wherein
7 +Be carbon seven and above hydrocarbon thereof;
B) in reaction zone, in the presence of catalyzer and under the effective reaction conditions, heavy arene generation hydro-dealkylation in the raw material, with light aromatics generation transalkylation reaction, light aromatics isomerization reaction and non-aromatics hydrocracking reaction, making feedstock conversion is to be rich in the light aromatics of benzene, toluene and dimethylbenzene and the stream I of light paraffins component;
C) stream I is separated and distillation by vapour-liquid, reclaims light aromatics and light paraffins respectively, and the heavy ends circulation is returned and entered the reaction zone utilization;
Wherein used catalyzer comprises following component in parts by weight: a) at least a in 0.01～0.8 part of metal that is selected from Pt or Pd or the oxide compound; B) 99.2～99.99 parts be selected from and have at least a in the 10 yuan of rings or the Zeolite support in 12 yuan of annular distance cracks.
2. according to the described method of utilizing pyrolysis gasoline hydrogenation cracking fecund benzene and dimethylbenzene of claim 1, it is characterized in that the C of described feeding reaction zone
7 +The weight space velocity of raw material is 0.5～10 hour
-1, the hydrogen/hydrocarbon raw material in the described step a) is 0.5～10: 1 with molar ratio computing.
3. according to the described method of utilizing pyrolysis gasoline hydrogenation cracking fecund benzene and dimethylbenzene of claim 1, it is characterized in that the temperature of reaction in the step b) is 250～600 ℃, reaction pressure is 0.5～5.0MPa.
4. according to the described method of utilizing pyrolysis gasoline hydrogenation cracking fecund benzene and dimethylbenzene of claim 1, it is characterized in that raw material is selected from C
7 +Pyrolysis gasoline raw material or C
7 +Gasoline stocks and toluene, reformation C
7 +The mixture of aromatic hydrocarbons, catalytic cracking cut.
5. according to the described method of utilizing pyrolysis gasoline hydrogenation cracking fecund benzene and dimethylbenzene of claim 1, it is characterized in that the boiling point according to compound is separated into benzene,toluene,xylene and C respectively in the step c)
9 +Cut, be specially that stream I is separated by vapour-liquid and distillation feeds the vapour-liquid separator, to obtain comprising first overhead stream of hydrogen, methane, ethane and LPG component and to comprise aromatic component and first tower base stream of small quantity of hydrogen and non-aromatic component reclaims liquefied petroleum gas (LPG) from first overhead fraction; First tower base stream is fed in the distillation tower, with second tower base stream that obtains to comprise second overhead stream of remaining hydrogen and non-aromatic component and comprise aromatic component; From second overhead stream, reclaim liquefied petroleum gas (LPG), and from described second tower base stream, reclaim aromatic component, gained toluene and C
9 +Cut returns as charging and proceeds to handle, wherein C
9 +Be carbon nine and above hydrocarbon thereof.
6. according to the described method of utilizing pyrolysis gasoline hydrogenation cracking fecund benzene and dimethylbenzene of claim 1, it is characterized in that also containing in the catalyzer at least a in the metal that is selected from Cu, Sn, Pb, Zn or Fe or the oxide compound, its consumption with parts by weight count＞0～1 part.
7. according to the described method of utilizing pyrolysis gasoline hydrogenation cracking fecund benzene and dimethylbenzene of claim 1, the metal or at least a consumption in the oxide compound that it is characterized in that being selected from parts by weight Pt or Pd are 0.01～0.5 part.
8. according to the described method of utilizing pyrolysis gasoline hydrogenation cracking fecund benzene and dimethylbenzene of claim 1, it is characterized in that the Zeolite support that Zeolite support is selected the binder free zeolite for use or used binding agent to be shaped, zeolite type is mordenite or ZSM-5.
9. according to the described method of utilizing pyrolysis gasoline hydrogenation cracking fecund benzene and dimethylbenzene of claim 1, it is characterized in that the SiO of zeolite
2/ Al
2O
3Mol ratio is 10～200.
10. according to the described method of utilizing pyrolysis gasoline hydrogenation cracking fecund benzene and dimethylbenzene of claim 9, it is characterized in that the SiO of zeolite
2/ Al
2O
3Mol ratio is 20～100.
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