CN104107717B - Improve toluene disproportionation catalyst of dimethylbenzene selective and application thereof - Google Patents
Improve toluene disproportionation catalyst of dimethylbenzene selective and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of toluene disproportionation catalyst improving dimethylbenzene selective and application thereof, mainly solve the technical problem that benzene selective is high, dimethylbenzene selective is low present in existing toluene disproportionation technology.The present invention includes 30～90 parts of SiO by using in terms of parts by weight2/Al2O3Mol ratio is the technical scheme of at least one the composition catalyst having in the molecular sieve of MWW structure, the binding agent of 10～70 parts and 0.01 ~ 10 part of group vib metal and mixture, 0.01 ~ 8 part of modifying element Zn and 0.02 ~ 6 part of modifying element La or Ce of 10～200, preferably solve this problem, can be used in the commercial production that toluene disproportionation produces benzene and dimethylbenzene.
Description
Technical field
The present invention relates to a kind of toluene disproportionation catalyst and application thereof, particularly have and improve dimethylbenzene selective performance
Toluene disproportionation catalyst.
Background technology
Aromatic hydrocarbons is important Organic Chemicals, is the most all derived from petrochemical industry.Wherein, benzene and dimethylbenzene master
To react from catalytic reforming, drippolene and toluene disproportionation and transalkylation.In three kinds of isomers of dimethylbenzene, to diformazan
Benzene (PX) is important Organic Chemicals, and mainly for the production of p-phthalic acid (PTA), PTA is again the former of production polyester
Material.Owing to PX demand is growing, directly extract from reformate and drippolene and separate PX far from meeting demand.
In benzene, toluene and dimethylbenzene, the source of toluene is the most sufficient, but its purposes can not show a candle to benzene and dimethylbenzene, therefore causes toluene phase
To surplus.Toluene is mainly derived from the virtue that reformer, drippolene and cinnamic by-product, coal liquefaction or coal gasification process prepare
Also containing substantial amounts of toluene in hydrocarbon, within 2011, global toluene production capacity has reached 29,540,000 tons.In China, toluene is mainly used as gasoline group
Divide, be disproportionated benzene processed and the raw material of dimethylbenzene, produce Methylnitrobenzene, benzoic acid, toluidines, Benzene Chloride, toluene di-isocyanate(TDI) first
The chemical products such as phenol and be used as solvent.Due to environmental protection pressure, toluene demand in terms of solvent will necessarily be restricted.
The most industrialized xylol production technology mainly has two kinds at present, a kind of by after toluene disproportionation and transalkylation
Producing xylol technique through adsorbing separation, isomerization, the second is selective disproportionation of toluene crystallization separation process.The former is through discrimination
Change and transalkylation are balanced the mixed xylenes of composition, though the latter can produce high-purity PX, but toluene conversion is low.
For adapting to energy-saving and cost-reducing requirement, improve the economic benefit of Aromatic Hydrocarbon United Plant, develop new volume increase PX production line gesture must
OK.
Toluene disproportionation unit is ingredient indispensable in Aromatic Hydrocarbon United Plant, and it can turn relatively inexpensive toluene
Turn to be worth higher dimethylbenzene and benzene, have logistics conversion hinge and effectively adjust the important work of aroamtic hydrocarbon raw material and product structure
With.Toluene disproportionation process mainly has two classes, i.e. comprises toluene and the C of transalkylation performance9The disproportionation of A aromatic hydrocarbons and transalkylation work
The toluene disproportionation process of skill and only process toluene.
Disproportionation is to utilize toluene and heavy aromatics to be converted into benzene and dimethylbenzene with the advantage of alkyl transfering process, and typical process is such as
" Tatoray " and " S-TDT " technique, along with the update of catalyst, disposal ability also gradually steps up, as HLD-001 is catalyzed
The air speed of agent is up to 1.7 h-1, the air speed of HAT-099 catalyst and MXT-01 catalyst reaches 2.5 h-1, hydrogen hydrocarbon mole simultaneously
Than also dropping to 3 ~ 4, total conversion maintains more than 45%.
Only process the toluene disproportionation process of toluene and include methylbenzene shape selective disproportionation technique and not selective disproportionation technique.Use toluene
Selective disproportionation technology such as MSTDP, MTPX technique, PX-Plus and SD technique etc., the available PX content mixed diformazan more than 90%
Benzene, has broken thermodynamical equilibrium, and air speed may be up to 3.5-4.0 h simultaneously-1, but conversion ratio is only about 30%.This technique needs to coordinate
Crystallization Separation could embody its superiority further.If dimethylbenzene is separated or is carried out by adsorbing separation, owing to toluene follows
Circular rector is higher, PX selectivity improve the advantage bringing separating energy consumption to reduce and to give a discount.Existing non-shape-selective toluene disproportionation technology
All there is low-speed, high hydrogen hydrocarbon mol ratio (hereinafter referred to as hydrogen-hydrocarbon ratio) causes the technical problem that production capacity is low, energy consumption is high.
CN 101124186 A use nickel modified mordenite be catalyst, need first catalyst is carried out good cure with
Passivation active nickel, the most just can carry out toluene disproportionation process.And this catalyst comprises the noble metal such as platinum, palladium, make catalyst raw
Product cost improves.For making toluene conversion be 47%, the hydrogen-hydrocarbon ratio of needs is 3:1.
CN 101687729 A uses nickel modified mordenite to be catalyst, and its Feed space velocities LHSV is 1 ~ 4.5 h-1, instead
Answer temperature 300 ~ 450 DEG C, reaction pressure 30 ~ 45 bar, hydrogen-hydrocarbon ratio at least 3:1.Meanwhile, this catalyst is also required to presulfurization process.
CN 102123947 A develops containing niobium mordenite catalyst, non-aromatized in toluene disproportionation process, product
Compound selectivity is less than 0.75%.
Toluene disproportionation process refers to that two molecule toluene generate a part benzene and the reaction of a part dimethylbenzene, 2 rubs in theory
Your toluene disproportionation generates mol ratio X/B of dimethylbenzene and benzene in the dimethylbenzene of 1 mole and the benzene of 1 mole, i.e. product and should be 1.
But in real reaction system, it is often accompanied by side reaction, as Toluene Hydrogenation dealkylation generates benzene and methane, toluene phenyl ring
It is hydrogenated to hexahydrotoluene, aromatic ring cracking reaction etc..Therefore, toluene disproportionation process is often the selection of benzene under normal circumstances
Property apparently higher than dimethylbenzene selective so that X/B be much smaller than 1.Benzene relative surplus in terms of the angle of market, dimethylbenzene is not then for should
Ask, it is desirable to reduce side reaction as far as possible, improve dimethylbenzene selective.
In conventional toluene disproportionation catalyst active component, modenite has one-dimensional twelve-ring channel design, acid
Intensity is high, is thus advantageous to the side reaction such as hydro-dealkylation and cracking, and therefore dimethylbenzene yield is the highest.ZSM-5 then has
Two dimension ten-ring cross channel structure, acid strength is higher, is extended influence, and is easier to Toluene Hydrogenation dealkylation.
The molecular sieve with MWW structure includes that MCM-22, MCM-36, MCM-49, MCM-56, ITQ-1 and ITQ-2 etc. are several
Kind, its crystal is generally lamellar or disk like, and (Wu has friendly relations, the structure of Xu Ning, MCM-22 family molecular sieves and catalytic performance, and chemistry is logical
Report, 2004,67, w102).
MCM-22 has two not connected multidimensional pore canal system.Article one, it is the sinusoidal reticulated channel of two dimension, for ten-ring
Aperture；Another is all ten-ring, but containing big supercage.Supercage is twelve-ring along horizontal section, cage size is 0.71 ×
0.71×1.82 nm.The sinusoidal pore canal system of MCM-22 is netted, has substantial amounts of cross point, is similar to ZSM-5.Molecule can
There to be various ways to be diffused in duct.But due to aperture ovalize, molecule is diffused with stronger restriction, is urging
Change in reaction and may show the strongest shape selectivity.
Catalyst with MCM-22 as carrier at alkane transformations as alkene with aromatic hydrocarbons, catalytic cracking, isomerisation of olefin, hydro carbons
The fields such as alkylation show good catalytic performance.
With benzene and ethylene as raw material in EP 0800497, compared with Y, Beta, ZSM-5 equimolecular sieve, at MCM-22, MCM-
When carrying out liquid phase alkylation reaction on 49 and MCM-56, show higher ethylbenzene selectivity.USP 5258565 also discloses that
MCM-36 molecular sieve prepares the technology of ethylbenzene for benzene and ethylene alkylation.
ZL 200410000957.2 discloses a kind of halogen-containing MCM-22 zeolite catalyst, for benzene liquid-phase alkylation
During reaction, ethylbenzene selectivity can be improved.A kind of dilute ethylene disclosed in CN101352690 and producing phenylethane from alkylation of benzene molecular sieve catalytic
Agent, is made up of MCM-22 or MCM-49.
USP 5557024 uses MCM-56 to prepare dividing of isopropylbenzene as a kind of high activity benzene and propylene liquid-phase alkylation
Sub-sieve catalyst, is 20 ~ 30 h in propylene air speed-1Time can obtain more than 90% propylene conversion.
USP 5258566 then discloses benzene and long chain olefin alkylation on MCM-36 molecular sieve and prepares chain alkyl fragrance
The technology of hydrocarbon, monoalkylation benzene selective is up to 81%.USP 5401896 uses MCM-49 as benzene and long chain olefin alkylation
Catalyst also yields good result.
CN101940943A discloses a kind of toluene and the form selected methylation catalyst of propylene synthesis p-Methylisopropylbenzene, bag
Containing the ZSM-35 through liquid-phase silicone deposition surface modification, Beta, MCM-22 zeolite.
USP 5254792 use MCM-22 and MCM-49 be catalyst carry out alkene and isoparaffin alkylation react with
Phase improves octane number, achieves preferable effect.USP 5258569 then uses MCM-36 to be that catalyst carries out isoparaffin
Alkylated reaction with linear alkene.
For increasing octane number, reduce harmful gas emission in motor-vehicle tail-gas, need to add in the oil MTBE
(tertiary butyl ether), ETBE (ethyl tert-butyl oxide) etc. are as gasoline additive, and this substantial amounts of isobutene. of needs is as raw material, feasible
One of approach is that abundant butene-1 resource is carried out skeletal isomerization to obtain isobutene..
Document (" Appl. Catal., A:General ", 1996,158:561 ~ 569) reports, and MCM-22 exists
This reaction has the highest activity, selectivity and stability, 1.15), when the conversion ratio of n-butene controls below 50%,
Selective isobutene is the highest.
ZL 99112884.2 uses modified MC M-22 molecular sieve to be that catalyst is for direct synthesis of arene with methane, Ke Yigao
Selectivity benzene.CN1401431 discloses a kind of methane aromatization catalyst, and this catalyst is for support work on MCM-49 zeolite
Property component WO3Or MoO3, the wherein SiO of MCM-492/Al2O3Ratio is 20～100.Its methane aromatization raw material is pure methane
Or methane, carbon dioxide gas mixture, in the aromatic product that can obtain, benzene proportion can be close to 90%.
At present, the molecular sieve with MWW structure is not yet had to be used as the report of toluene disproportionation catalyst.
Summary of the invention
One of the technical problem to be solved is to overcome existing toluene disproportionation to prepare the skill of dimethylbenzene and benzene
Owing to occurring side reaction to cause the selectivity height of benzene, dimethylbenzene selective low present in art, product X/B is caused to be much smaller than 1
Technical problem, it is provided that a kind of have the toluene disproportionation catalyst improving dimethylbenzene selective performance.This catalyst is used for toluene discrimination
Change reaction, there is dimethylbenzene selective suitable with benzene selective, the advantage that toluene conversion is high.
The two of the technical problem to be solved are to provide the application of a kind of catalyst solving one of technical problem
Method.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of raising dimethylbenzene selective
Toluene disproportionation catalyst, in terms of parts by weight, including following components:
1) 30～90 parts of SiO2/Al2O3Mol ratio is the molecular sieve with MWW structure of 10～200；
2) at least one in 0.01 ~ 10 part of group vib metallic element；
3) at least one in 0.02 ~ 6 part of rare earth element；
4) binding agent of 10～70 parts.
In technique scheme, preferred technical scheme, have the molecular sieve of MWW structure selected from MCM-22, MCM-36,
At least one in MCM-49, MCM-56；Binding agent is selected from aluminium oxide, boehmite, Kaolin or montmorillonite at least
A kind of.Preferred technical scheme, the molecular sieve with MWW structure is selected from least in MCM-22, MCM-49 and MCM-56
Kind；There is the SiO of MWW structure molecular screen2/Al2O3Mol ratio is 15～100.Preferably technical scheme, with catalyst weight part
Number meter, catalyst comprisesThe content range of at least one in B race metallic element is 0.1 ~ 8 part.Preferably technical scheme,
In terms of catalyst weight number, catalyst also comprises at least one in the periodic table of elements of 0.01 ~ 8 part in II B-group element.
Preferred technical scheme, in the periodic table of elements, II B-group element is selected from zinc, and in terms of catalyst weight number, the content of zinc is
0.2 ~ 4 part.Rare earth element is selected from La or Ce, and in terms of catalyst weight number, the content range of rare earth element is 0.1 ~ 5 part.Excellent
The technical scheme of choosing, group vib metallic element is selected from molybdenum or tungsten, in terms of catalyst weight number, molybdenum or the content range of wolfram element
It it is 0.1 ~ 5 part.
For solving the two of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of raising dimethylbenzene selective
Toluene disproportionation process, under hydro condition, with toluene as raw material, reaction temperature 300～500 DEG C, reaction pressure 0.1～
5.0 MPa, hydrogen/toluene mole ratio 0.2～4, Feed space velocities 1～8 h-1Under the conditions of, raw material and above-mentioned any one are urged
Agent contacts, and reaction generates dimethylbenzene and benzene.
In technique scheme, the preferred scope of reaction temperature is 350～450 DEG C, the preferred scope of reaction pressure be 0.5～
4.0 MPa, the preferred scope of hydrogen/toluene mole ratio is 0.5～3, and the preferred scope of Feed space velocities is 2～6 h-1.Preferably technology
Scheme is, in product, dimethylbenzene and mol ratio X/B of benzene are more than 0.9.
Due to the fact that and use the molecular sieve with MWW structure as the active component of catalyst, be not the most that there is MWW knot
The MCM-22 molecular sieve of structure, has two not connected multidimensional pore canal system, and one is the sinusoidal reticulated channel of two dimension, is ten yuan
Annular aperture；Another is all ten-ring, but containing big supercage, supercage is twelve-ring along horizontal section, and cage size is 0.71
×0.71×1.82 nm.The sinusoidal pore canal system of MCM-22 is netted, has substantial amounts of cross point, and molecule can have multiple side
Formula is diffused in duct.But due to aperture ovalize, molecule is diffused with stronger restriction, can in catalytic reaction
The strongest shape selectivity can be shown.MCM-22 molecular sieve is that the catalyst of active component is alkene and aromatic hydrocarbons at alkane transformations, urges
Change the fields such as cracking, isomerisation of olefin, hydro carbons alkylation and show good catalytic performance.
The high selective toluene disproportionation catalyst of dimethylbenzene using the present invention to provide, reaction temperature 300～500 DEG C,
Reaction pressure 0.1～5.0 MPa, toluene feed air speed 1～8 h-1, under the conditions of hydrogen and toluene mole ratio 0.2～4, toluene turns
Rate reaches as high as 46.1%, and X/B reaches as high as 0.98, and benzene and C8 aromatic hydrocarbons (B+C8) selectivity reach as high as 86.8%, achieve
Preferably technique effect.
Below by embodiment, the invention will be further elaborated, but the most therefore limits the scope of the invention.
Detailed description of the invention
[embodiment 1]
Take SiO2/Al2O3Mol ratio is 60 grams of Hydrogen MCM-22 molecular sieve, boehmite 40 grams and the ammonium tetramolybdate of 20
[(NH4)2Mo4O13·2 H2O] 12.9 grams (equivalent 7.5 grams of molybdenums), add 5 milliliters and 50 grams water of chemical pure nitric acid after mix homogeneously,
Carry out extruded moulding after mediating uniformly, 120 DEG C dry 4 hours after use Zn(NO3)2And La(NO3)3Mixed solution impregnates, after drying
In 600 DEG C of roastings 4 hours, preparing catalyst A, through elementary analysis, recording Mo content is 7.5%, and Zn content is 0.5%, La content
It is 0.3%.
[embodiment 2]
Take SiO2/Al2O3Mol ratio is 85 grams of Hydrogen MCM-22 molecular sieve, Kaolin 15 grams and the ammonium paratungstate of 92
[H40N10W12O41] 1.7 grams (equivalent 0.2 gram of tungsten), add 5 milliliters and 50 grams water of chemical pure nitric acid after mix homogeneously, mediate uniformly
After carry out extruded moulding, 120 DEG C dry 4 hours after use Zn(NO3)2And Ce(NO3)2Mixed solution impregnates, in 600 DEG C after drying
Roasting 4 hours, prepares catalyst B, and through elementary analysis, recording W content is 0.2%, and Zn content is 4.5%, and Ce content is 1.2%.
[embodiment 3]
Take SiO2/Al2O3Mol ratio is 70 grams of Hydrogen MCM-49 molecular sieve, aluminium oxide 30 grams and the chromic nitrate [Cr of 40
(NO3)3·9H2O] after 15.3 grams of (equivalent 2 grams of chromium) mix homogeneously, add 2 milliliters and 50 grams water of chemical pure nitric acid, mediate uniformly
After carry out extruded moulding, 120 DEG C dry 4 hours after use Zn(NO3)2And La(NO3)3Mixed solution impregnates, in 600 DEG C after drying
Roasting 4 hours, prepares catalyst C, and through elementary analysis, recording Cr content is 2%, and Zn content is 2%, and La content is 4.5%.
[embodiment 4]
Take SiO2/Al2O340 grams of the Hydrogen MCM-49 molecular sieve of mol ratio 25, boehmite 60 grams and ammonium tetramolybdate
[(NH4)2Mo4O13·2 H2O] after 8.6 grams of (equivalent 5 grams of molybdenums) mix homogeneously, add 2 milliliters and 50 grams water of chemical pure nitric acid, pinch
Carry out extruded moulding after closing uniformly, 120 DEG C dry 4 hours after use Zn(NO3)2And La(NO3)3Mixed solution impregnate, after drying in
600 DEG C of roastings 4 hours, prepare catalyst D, and through elementary analysis, recording Mo content is 5%, and Zn content is 2. 5%, and La content is
5%。
[embodiment 5]
Take SiO2/Al2O370 grams of the Hydrogen MCM-36 molecular sieve of mol ratio 40, boehmite 30 grams and ammonium dimolybdate
[(NH4)2Mo2O7] after 5.2 grams of (equivalent 3 grams of molybdenums) mix homogeneously, add 2 milliliters and 50 grams water of chemical pure nitric acid, after mediating uniformly
Carry out extruded moulding, 120 DEG C dry 4 hours after use Zn(NO3)2And La(NO3)3Mixed solution impregnates, in 600 DEG C of roastings after drying
Burning 4 hours, prepare catalyst E, through elementary analysis, recording Mo content is 3%, and Zn content is 1. 5%, and La content is 1.5%.
[embodiment 6]
Take SiO2/Al2O370 grams of the Hydrogen MCM-56 molecular sieve of mol ratio 54, boehmite 30 grams and ammonium dimolybdate
[(NH4)2Mo2O7] after 2.6 grams of (equivalent 1.5 grams of molybdenums) mix homogeneously, add 2 milliliters and 50 grams water of chemical pure nitric acid, mediate uniformly
After carry out extruded moulding, 120 DEG C dry 4 hours after use Zn(NO3)2And La(NO3)3Mixed solution impregnates, in 600 DEG C after drying
Roasting 4 hours, prepares catalyst F, and through elementary analysis, recording Mo content is 1.5%, and Zn content is 1. 5%, and La content is 1.5%.
[embodiment 7]
Take SiO2/Al2O360 grams, 40 grams montmorillonites of the Hydrogen MCM-22 molecular sieve of mol ratio 20 and ammonium dimolybdate [(NH4)2Mo2O7] after 2.6 grams of (equivalent 1.5 grams of molybdenums) mix homogeneously, add 2 milliliters and 50 grams water of chemical pure nitric acid, carry out after mediating uniformly
Extruded moulding, dries after 4 hours for 120 DEG C and uses Zn(NO3)2And La(NO3)3Mixed solution impregnates, in 600 DEG C of roastings 4 after drying
Hour, prepare catalyst G, through elementary analysis, recording Mo content is 1.5%, and Zn content is 1. 5%, and La content is 3%.
[embodiment 8]
Take SiO2/Al2O360 grams, 40 grams aluminium oxidies of the Hydrogen MCM-22 molecular sieve of mol ratio 36 and ammonium tetramolybdate [(NH4)2Mo4O13·2 H2O] after 8.6 grams of (equivalent 5 grams of molybdenums) mix homogeneously, add 2 milliliters and 50 grams water of chemical pure nitric acid, mediate uniformly
After carry out extruded moulding, 120 DEG C dry 4 hours after use Zn(NO3)2And La(NO3)3Mixed solution impregnates, in 600 DEG C after drying
Roasting 4 hours, prepares catalyst H, and through elementary analysis, recording Mo content is 5%, and Zn content is 2. 5%, and La content is 1.3%.
[embodiment 9]
Take SiO2/Al2O340 grams of the Hydrogen MCM-22 molecular sieve of mol ratio 20, SiO2/Al2O3The Hydrogen MCM-of mol ratio 40
56 40 grams of molecular sieves, boehmite 20 grams and ammonium dimolybdate [(NH4)2Mo2O7] 2.6 grams of (equivalent 1.5 grams of molybdenums) mix homogeneously
After, add 2 milliliters and 50 grams water of chemical pure nitric acid, after mediating uniformly, carry out extruded moulding, 120 DEG C dry 4 hours after use Zn
(NO3)2And La(NO3)3Mixed solution impregnates, and in 600 DEG C of roastings 4 hours after drying, prepares catalyst I, through elementary analysis, surveys
Obtaining Mo content is 1.5%, and Zn content is 3%, and La content is 3%.
[embodiment 10～18]
The catalyst A-I prepared by embodiment 1-9, carries out toluene disproportionation process Performance at fixed bed reactors, comments
Valency condition is: with pure toluene as raw material, loaded catalyst 10 grams, and toluene feed weight space velocity is 2.5 hours-1, reaction temperature
390 DEG C, reaction pressure 3.0 MPa, hydrogen and methylbenzene raw material molecular proportion 2.0, evaluation result is as shown in table 1.
Toluene conversion, the toluene amount of the toluene amount of wt %=100 × react away/enter reactor.
Selectivity, the toluene amount that the benzene (B) of wt %=100 × generation and dimethylbenzene (X) are measured/reacted away.
The benzene mole number of dimethylbenzene molal quantity/generation that X/B, mol/mol=generate.
Table 1
| Embodiment | Catalyst is numbered | Toluene conversion | Selectivity | X/B |
| 10 | A | 45.8 | 79.8 | 0.92 |
| 11 | B | 44.1 | 80.5 | 0.94 |
| 12 | C | 43.7 | 82.0 | 0.97 |
| 13 | D | 44.5 | 81.5 | 0.96 |
| 14 | E | 45.5 | 82.3 | 0.94 |
| 15 | F | 43.9 | 81.5 | 0.95 |
| 16 | G | 44.2 | 81.7 | 0.98 |
| 17 | H | 45.4 | 80.4 | 0.94 |
| 18 | I | 45.5 | 81.2 | 0.95 |
[embodiment 19～24]
With pure toluene as raw material, having investigated the toluene disproportionation process performance of catalyst H at fixed bed reactors, catalyst fills
The amount of filling out 10 grams, differential responses condition and reaction result are listed in table 2.
Table 2
| Embodiment | 19 | 20 | 21 | 22 | 23 | 24 |
| Reaction temperature/DEG C | 320 | 360 | 380 | 400 | 420 | 480 |
| Reaction pressure/MPa | 0.5 | 2.0 | 3.0 | 3.0 | 3.0 | 4.0 |
| Feed space velocities/h-1 | 1.2 | 1.7 | 2.0 | 3.0 | 4.0 | 7.5 |
| Hydrogen/toluene mole ratio | 0.5 | 1.0 | 1.5 | 2.5 | 3.0 | 3.8 |
| X/B | 0.99 | 0.98 | 0.96 | 0.95 | 0.94 | 0.91 |
| Toluene conversion | 28.8 | 37.5 | 42.9 | 46.1 | 45.8 | 42.6 |
| Selectivity | 86.8 | 86.3 | 84.3 | 82.8 | 80.6 | 74.2 |
Claims (10)
1. improve a toluene disproportionation catalyst for dimethylbenzene selective, in terms of parts by weight, including following components:
1) 30～90 parts of SiO2/Al2O3Mol ratio is the molecular sieve with MWW structure of 10～200；
2) at least one in 0.01 ~ 10 part of group vib metallic element；
3) at least one in 0.02 ~ 6 part of rare earth element；
4) binding agent of 10～70 parts.
The toluene disproportionation catalyst of raising dimethylbenzene selective the most according to claim 1, it is characterised in that there is MWW knot
At least one in MCM-22, MCM-36, MCM-49, MCM-56 of the molecular sieve of structure；Binding agent is selected from aluminium oxide, intends thin water
At least one in aluminum stone, Kaolin or montmorillonite.
The toluene disproportionation catalyst of raising dimethylbenzene selective the most according to claim 1, it is characterised in that there is MWW knot
At least one in MCM-22, MCM-49 and MCM-56 of the molecular sieve of structure；There is the SiO of MWW structure molecular screen2/Al2O3
Mol ratio is 15～100.
The toluene disproportionation catalyst of raising dimethylbenzene selective the most according to claim 1, it is characterised in that with catalyst
Parts by weight meter, catalyst comprisesThe content range of at least one in B race metallic element is 0.1 ~ 8 part.
The toluene disproportionation catalyst of raising dimethylbenzene selective the most according to claim 1, it is characterised in that with catalyst
Parts by weight meter, catalyst also comprises at least one in the periodic table of elements of 0.01 ~ 8 part in II B-group element.
The toluene disproportionation catalyst of raising dimethylbenzene selective the most according to claim 5, it is characterised in that period of element
In table, II B-group element is selected from zinc, and in terms of catalyst weight number, the content of zinc is 0.2 ~ 4 part.
The toluene disproportionation catalyst of raising dimethylbenzene selective the most according to claim 1, it is characterised in that rare earth element
Selected from La or Ce, in terms of catalyst weight number, the content range of rare earth element is 0.1 ~ 5 part；Group vib metallic element is selected from molybdenum
Or tungsten, in terms of catalyst weight number, the content range of molybdenum or wolfram element is 0.1 ~ 5 part.
8. improve a toluene disproportionation process for dimethylbenzene selective, under hydro condition, with toluene as raw material, in reaction temperature
300～500 DEG C, reaction pressure 0.1～5.0 MPa, hydrogen/toluene mole ratio 0.2～4, Feed space velocities 1～8 h-1Under the conditions of,
Raw material contacts with any one catalyst in claim 1 to 7, and reaction generates dimethylbenzene and benzene.
The toluene disproportionation process of raising dimethylbenzene selective the most according to claim 8, it is characterised in that reaction temperature 350
～450 DEG C, reaction pressure 0.5～4.0 MPa, hydrogen/toluene mole ratio 0.5～3, Feed space velocities 2～6 h-1。
The toluene disproportionation process of raising dimethylbenzene selective the most according to claim 8, it is characterised in that diformazan in product
Benzene is more than 0.9 with mol ratio X/B of benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310130184.9A CN104107717B (en) | 2013-04-16 | 2013-04-16 | Improve toluene disproportionation catalyst of dimethylbenzene selective and application thereof |
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| CN201310130184.9A CN104107717B (en) | 2013-04-16 | 2013-04-16 | Improve toluene disproportionation catalyst of dimethylbenzene selective and application thereof |
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| CN1341078A (en) * | 1999-01-21 | 2002-03-20 | 埃克森美孚石油公司 | Synthetic porous crystalline MCM-68, its synthesis and use |
| CN1721069A (en) * | 2004-07-12 | 2006-01-18 | 中国石油化工股份有限公司 | Catalyst for toluene disproportionation and alkyl transfer |
| CN1835798A (en) * | 2003-07-23 | 2006-09-20 | 埃克森美孚化学专利公司 | High temperature calcination of selectivated molecular sieve catalysts for activity and diffusional modification |
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| CN1341078A (en) * | 1999-01-21 | 2002-03-20 | 埃克森美孚石油公司 | Synthetic porous crystalline MCM-68, its synthesis and use |
| CN1835798A (en) * | 2003-07-23 | 2006-09-20 | 埃克森美孚化学专利公司 | High temperature calcination of selectivated molecular sieve catalysts for activity and diffusional modification |
| CN1721069A (en) * | 2004-07-12 | 2006-01-18 | 中国石油化工股份有限公司 | Catalyst for toluene disproportionation and alkyl transfer |
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