CN103551187B - A kind of catalyst producing toluene and C8 aronmatic and its preparation method and application - Google Patents
A kind of catalyst producing toluene and C8 aronmatic and its preparation method and application Download PDFInfo
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- CN103551187B CN103551187B CN201310511890.8A CN201310511890A CN103551187B CN 103551187 B CN103551187 B CN 103551187B CN 201310511890 A CN201310511890 A CN 201310511890A CN 103551187 B CN103551187 B CN 103551187B
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Abstract
A kind of with benzene and heavy aromatics for raw material production toluene and the catalyst of C8 aronmatic, described catalyst includes 1 25wt%MOR zeolite, 1 65wt%ZSM 5 zeolite, at least one periodic table of elements VA race element of 0.01 3.0wt%, at least one periodic table of elements the VIIIth race's element and binding agent of surplus of 0.01 2.0wt%；Wherein, described MOR zeolite and ZSM 5 zeolite all contain silicon and at least one is selected from aluminum, ferrum, gallium and the element T of boron, and total Si/T atomic ratio is more than 5.Additionally, present invention also offers the preparation method and application of this catalyst.Catalyst of the present invention has good mechanical strength and fabulous catalytic performance.
Description
Technical field
The present invention relates to a kind of with benzene and heavy aromatics for raw material production toluene and the catalyst of C8 aronmatic and preparation side thereof
Method and application.
Background technology
Along with the fast development of petrochemical industry, in aromatic hydrocarbons field, benzene (B) and heavy aromatics, especially carbon more than ten weight
Aromatic hydrocarbons (C10 +Aromatic hydrocarbons) comprehensive utilization more and more important: on the one hand, along with sending out of the increase of each enterprise ethylene unit and Coal Chemical Industry
Exhibition, the yield of benzene is continuously increased, and meanwhile, the domestic requirement to Determination of Benzene In Gasoline is increasingly strict, causes domestic purified petroleum benzin yield more
Come the biggest.According to incompletely statistics, 2012 annual productions are more than 11,000,000 tons, and the downstream product such as aniline, phenol-acetone, styrene
Demand is at about 9,000,000 tons/year, and therefore, the easy situation in purified petroleum benzin market is by long-term existence, it is necessary to find new for it
Application.In terms of actual market situation, the growth of yield, market price are unable to catch up with in the growth of the nearly 2 years purified petroleum benzin market demands
Lattice are always in the trend glided, and therefore, use toluene disproportionation process route, utilize valuable toluene resource to produce low value-added
Benzaldehyde product, more and more uneconomical；On the other hand, owing to new PX project goes into operation successively, some old isomerization units are carried out
Transformation, causes C8 aronmatic (C8Aromatic hydrocarbons) resource is more and more nervous, and price remains high always.
The most domestic utilization for heavy aromatics, or carry out dismutation reaction, or (heavy aromatics is light to carry out dealkylation
Matter technology).And first above-mentioned technology there is problems in that, it is impossible to benzene as raw material, the most more or less will produce benzene；
Secondly, heavy aromatics utilize primary limitation at C9 aromatic (C9Aromatic hydrocarbons), to C10 +Aromatic hydrocarbons utilizes very limited.
Therefore, how to utilize existing benzene and heavy aromatics, produce toluene and C8Aromatic hydrocarbons, arouses people's interest the most day by day.
At present, the most it is not correlated with the report of mature technology.
Chinese patent application CN1443736A and CN1443737A disclose a kind of benzene and carbon nine and above accordance thereof
The catalyst of transfer and the arene transalkylation method of this catalyst of employing.Described catalyst includes the hydrogen that silica alumina ratio is 3-500
Type zeolite 10-80 part, the metal of the molybdenum being loaded on zeolite and/or oxide 0.01-20 part and binding agent 10-90 part.But institute
State the limited in one's ability of catalyst treatment carbon ten and above heavy aromatics.
It is also mentioned that a kind of method that shifts of benzene and carbon nine and above accordance in Chinese patent application CN1884238A
And catalyst；But there is the problem that transalkylation reaction activity and selectivity is low in said method and catalyst.
Chinese patent application CN1506341A is referred to a kind of process producing dimethylbenzene with benzene and C9 aromatic.
In the method, the solid phase fixed bed reactor of gas, the catalyst used 10-90 weight portion Han h-type zeolite, and zeolite are used
Silica alumina ratio be 3-500, zeolite loads the metal of bismuth or/and oxide 0.05-10 weight portion, and selected from chromium, zirconium, tungsten,
At least one metal in lanthanum, rhenium or silver is or/and oxide 0.1-10 part, binding agent aluminium oxide 10-60 part.But this patented technology
Only relate to benzene react with C9 aromatic, fail to solve carbon ten and the process problem of above heavy aromatics.
Summary of the invention
An object of the present invention is: provide a kind of aromatic hydrocarbons with good mechanical strength and catalytic perfomance to turn
Shifting catalyst.
In order to realize foregoing invention purpose, technical scheme provided by the present invention is as follows: a kind of is former with benzene and heavy aromatics
Material produces toluene and the catalyst of C8 aronmatic, counts with catalyst weight for 100wt%, and described catalyst includes 1-25wt%MOR
Zeolite, 1-65wt%ZSM-5 zeolite, at least one periodic table of elements VA race element of 0.01-3.0wt% (" physico learn to do
Volume ", the 76th edition), at least one periodic table of elements the VIIIth race's element (" physical chemistry handbook ", the 76th edition) of 0.01-2.0wt%
Binding agent with surplus；Wherein, described MOR zeolite and ZSM-5 zeolite all contain silicon and at least one is selected from aluminum, ferrum, gallium and boron
Element T, and total Si/T atomic ratio is more than 5.
In catalyst of the present invention, described MOR zeolite at least partially its acid form, the most almost it is entirely its acid
Form；This zeolite contain silicon and at least one selected from aluminum, ferrum, gallium and the element T of boron, and described T element be preferably aluminum and/or
Boron；The total Si/T atomic ratio of this zeolite is more than 5, preferably in the range of 5-300, further preferably in the range of 10-150.
In catalyst of the present invention, described ZSM-5 zeolite at least partially its acid form, the most almost it is entirely it
Acid form；This zeolite contain silicon and at least one selected from aluminum, ferrum, gallium and the element T of boron, and described element T be preferably aluminum and/or
Boron；The total Si/T atomic ratio of this zeolite is more than 5, preferably in the range of 5-300, further preferably in the range of 10-150.
In catalyst of the present invention, described zeolite is at least partly, to be the most almost entirely acid form, i.e. hydrogen (H+) zeolite of type.Sodium content in zeolite is that Na/T atomic ratio is less than 0.5, preferably shorter than 0.1, more preferably less than 0.02.
In catalyst of the present invention, it is preferable that described VA race metal is selected from antimony and bismuth；Described group VIII metal selects
From platinum and palladium.
In the present invention, if no special instructions, described " being selected from " be selected from described in list one or more in material.
In catalyst of the present invention, described binding agent is selected from natural clay, synthesis of clay, magnesium oxide, aluminium oxide, oxygen
At least one in SiClx, silica-alumina, titanium oxide, boron oxide, zirconium oxide, aluminum phosphate, titanium phosphate and zirconium phosphate, excellent
Choosing is made up of the material of aluminium oxide and clay.Described natural clay preferably Kaolin, bentonite etc. is conventional does catalyst bonding
The material of agent.
In catalyst of the present invention, the VIIIth described race and VA race metallic element are well dispersed into catalyst
Surface, preferred deposition on the adhesive, and is distributed in the granule of catalyst the most well.By chemisorbed,
Such as H2-O2Titration or carbon monoxide absorption, the dispersion of the described group VIII metal of measurement is in the range of 50-100%.Described
Macroscopical breadth coefficient of group VIII metal is in the range of 0.7-1.3.Described macroscopic view breadth coefficient is by using Castaing microprobe
The scattergram measured obtains, and is defined as the content of metal described in particle cores and the ratio of grain edges content.The footpath of this catalyst
To crushing strength more than 80N cm-1。
Another object of the present invention is to: provide above-mentioned with urging that benzene and heavy aromatics are raw material production toluene and C8 aronmatic
The preparation method of agent.
Provided by the present invention with benzene and heavy aromatics for raw material production toluene and the preparation method of the catalyst of C8 aronmatic
Comprise the steps:
(1) MOR zeolite and ZSM-5 zeolite carrying out pretreatment, the organic formwork agent in removing zeolite micropore, then with extremely
Few a kind of ammonium salt solution carries out ion-exchange step at least one times, to remove the alkali metal cation in zeolite；
(2) by the zeolite hybrid shaping after binding agent and above-mentioned process, it is prepared as extrudate or spherical；
(3) it is dried at a temperature of ambient temperature to 250 DEG C, then in air or oxygen, the temperature of 250-600 DEG C
Under carry out roasting；
(4) make at least one VA race element and at least one the VIIIth race's element deposition catalyst after baking；
(5) in air or oxygen, roasting 0.5-10 hour at 250-600 DEG C, then in the atmosphere of hydrogen,
Reduce 1-10 hour at 300-600 DEG C, it is thus achieved that reduction-state catalyst.
The following detailed description of the preparation method of catalyst of the present invention, but the present invention is the most therefore and by any limit
System.
First can select and well known to a person skilled in the art that any method (such as roasting in dry air) processes institute
State zeolite, remove the organic formwork agent in zeolite micropore, then use at least one ammonium salt solution, such as NH4NO3Solution, carry out to
Few primary ions exchange step, to remove the alkali metal cation (particularly sodium ion) in zeolite, preferably removes nearly all
Alkali metal cation.
Then, by binding agent and above-mentioned zeolite hybrid shaping, catalyst is prepared.Catalyst of the present invention is preferably made extrusion
Thing or spherical.For every kind of binding agent, by well known to a person skilled in the art principle determine the molding condition of zeolite, pore former,
Incorporation time, extrusion pressure, dry rate and persistent period time catalyst makes extrudate, to obtain optimal catalysis
Agent.
Then, roasting at a temperature of 250-600 DEG C, preferably it is pre-dried, such as in ambient temperature to 250 DEG C, preferably
Dry at a temperature of 40-200 DEG C.Drying steps is carried out during preferably heating up needed for carrying out roasting.After roasting, gained is spherical
The radial direction crushing strength of the catalyst of thing or extrudate form is more than 80N cm-1。
The deposition of described metal can be carried out in any stage of preparation, can be before formation, it is also possible at zeolite with viscous
During mixture mixing, make what zeolite constituted with by the compound of this metal and binding agent totally to mix, the most after such shaping.When
Adding fashionable after shaping, metallic element can add before firing or afterwards, adds the most after firing.Metallic element can be complete
Portion is deposited on zeolite, it is possible to be deposited on zeolite and binding agent, it is possible to all deposition on the adhesive, is preferably completely deposited on
On binding agent.
The deposition of at least one group VIII metal element typically uses the methods such as dry leaching, excess dipping or ion exchange to enter
OK, generally use platinum and/or palladium salt, the competitive adsorbates such as hydrochloric acid while deposition, can be added.Platinum salt can be chloroplatinic acid, two
One or more in chlorine four ammino platinum, tetrachloro six ammino platinum or tetrachloro two ammino platinum；Palladium salt can be chloride or the nitre of palladium
Acid compounds, such as Palladous nitrate., dinitro four ammino palladium, palladium chloride, dichloride four ammino palladium or diamminodichloro close palladium
In one or more.
The deposition of at least one VA race metallic element can use the art technology such as dry leaching, excess dipping or ion exchange
Any deposition technique known to personnel adds, and can be added by following compound, such as chloride, bromide, sulfate and nitre
Hydrochlorate.VA race metallic element can be before group VIII metal element, add simultaneously or after.
After described metallic element deposition, in the atmosphere of air or oxygen, roasting 0.5-10 hour at 250-600 DEG C,
Preferably roasting 1-4 hour at a temperature of 350-550 DEG C.Then, in the atmosphere of hydrogen, the 1-10 that reduces at 300-600 DEG C is little
Time, reductase 12-5 hours at a temperature of preferably 350-550 DEG C, it is thus achieved that reduction-state catalyst.
As an example, a kind of method for optimizing preparing catalyst of the present invention is as follows: (general by mixing at wet matrix gel
At least one acid and powder adhesive obtain) mixed zeolite in such as aluminium oxide so that mixture obtains good uniformity, mixed
The conjunction time is about 10 minutes, then passes the mixture through mould and forms the extrudate of 0.4-4.0mm, preferably 0.4-2.5mm's
The extrudate of extrudate, more preferably 0.8-2.0mm.In the baking oven of about 120 DEG C after drying, about 400 DEG C of roastings 4 hours, connect
Deposition the VIIIth race and VA race element, such as platinum and bismuth, with chloroplatinic acid and nitre in the presence of competitive adsorbate (such as hydrochloric acid)
Acid bismuth solution impregnates, and carries out roasting, such as, about 400 DEG C of roastings about 2 hours, then reduce after deposition.
Another object of the present invention is to: providing above-mentioned is raw material production toluene and C8 aronmatic with benzene and heavy aromatics
The application of catalyst.
The application of described catalyst that the present invention provides is as follows: with benzene and heavy aromatics as raw material, exist at described catalyst
Under, at reaction temperature 300-500 DEG C, hydrogen partial pressure 1.0-3.5MPa, Feed space velocities (representing with kg charging/kg catalyst/h)
0.25-30h-1, under conditions of hydrogen hydrocarbon mol ratio 3.0-5.0, produce toluene and C8 aronmatic.
The application of catalyst provided by the present invention is described in detail further below, but the most therefore the present invention is taken office
What limits.
In above-mentioned application, described reaction temperature is preferably in the range of 320-450 DEG C, further preferably at 340-430
In the range of DEG C；Described hydrogen partial pressure is preferably in the range of 1.5-3.0MPa, further preferably in the scope of 2.0-2.8MPa
In；Described Feed space velocities is preferably at 1-10h-1In the range of, further preferably at 2-6h-1In the range of.
In application of the present invention, described raw material is selected from: benzene and the mixture of C9 aromatic, benzene and carbon nine and above virtue
The mixture of hydrocarbon, benzene and carbon ten and the mixture of above aromatic hydrocarbons.
Additionally, use " benzene conversion ratio " (B in the present inventionc), " carbon nine and above aromatics conversion rate thereof " (HAc) and " toluene
With C8 aronmatic (C8A) total recovery " (Yc) evaluate activity and the selectivity of catalyst.Its computing formula is as follows:
Compared with prior art, the beneficial effects are mainly as follows following aspect:
The catalyst that the present invention is prepared with spherical or extrudate form, has good mechanical strength, radially crushing strength
More than 80N cm-1。
In catalyst of the present invention, described group VIII and VA race metallic element are well dispersed into catalyst
Surface, and be distributed in the granule of catalyst the most well.By chemisorbed, such as H2-O2Titration or an oxygen
Changing carbon adsorption, the dispersion of the described group VIII metal of measurement is in the range of 50-100%.Described group VIII metal
Macroscopic view breadth coefficient is in the range of 0.7-1.3.
Catalyst of the present invention is for benzene and heavy aromatics, particularly with carbon ten and above heavy aromatics as raw material production
In the reaction of toluene and C8 aronmatic, there is fabulous catalytic performance.
Detailed description of the invention
Following instance is used for further describing the present invention, and the present invention is not therefore subject to any restriction.
Embodiment 1
By silica alumina ratio (SiO2/Al2O3, afterwards with) be 10 sodium form modenite be that 30 sodium form ZSM-5 zeolites divide with silica alumina ratio
Not Hun He after, in the aqueous solution of ammonium chloride, at 90 DEG C ion exchange 6 hours, filter off mother solution, repeat ion exchange 2-4 time,
Dry 2 hours in 120 DEG C after washing, obtain two kinds of mixing ammonium type zeolites.Two kinds of ammonium type zeolites mix with boehmite respectively
(modenite/ZSM-5 zeolite/quality of alumina ratio=25:25:50), adds dust technology and water, after mediating uniformly, is extruded into diameter
The cylindrical bar of 2.0mm.Two kinds of cylindrical bar are dried 2 hours at 120 DEG C in atmosphere, then roasting 2 hours at 250 DEG C,
At 500 DEG C, roasting 2 hours, obtain catalyst base.Two kinds of catalyst bases are immersed in containing hydrochloric acid, chloroplatinic acid and bismuth chloride
Solution in, then in air at 120 DEG C dry 2 hours, roasting 2 hours at 500 DEG C, obtain platinum content 0.5wt%, bi content
Two kinds of oxidized catalyst of 0.1wt%.Finally by two kinds of oxidized catalyst in hydrogen, reduce 4 hours at 500 DEG C, obtain
Catalyst A1.
Embodiment 2
The sodium form modenite that silica alumina ratio is 10 is mixed, according to embodiment with the sodium form ZSM-5 zeolite that silica alumina ratio is 150
The method of 1 carries out ion exchange, extruded moulding, roasting, dipping, roasting and reduction, obtains catalyst A2.
Embodiment 3
It is after 30 sodium form ZSM-5 zeolites mix by sodium form modenite that silica alumina ratio is 25 with silica alumina ratio, according to embodiment 1
Method carry out ion exchange, mix (modenite/ZSM-5 zeolite/quality of alumina ratio=5:45:50) with boehmite,
Carry out extruded moulding, roasting, dipping, roasting and reduction according to the method for embodiment 1, obtain platinum content 1.5wt%, bi content
The catalyst A3 of 0.1wt%.
Embodiment 4
It is after 150 sodium form ZSM-5 zeolites mix by sodium form modenite that silica alumina ratio is 25 with silica alumina ratio, according to embodiment
The method of 1 carries out ion exchange, mix with boehmite (modenite/ZSM-5 zeolite/quality of alumina ratio=5:45:
50), carrying out extruded moulding, roasting, dipping, roasting and reduction according to the method for embodiment 1, obtain platinum content 0.5wt%, bismuth contains
The catalyst A4 of amount 0.08wt%.
Embodiment 5
It is after 30 sodium form ZSM-5 zeolites mix by sodium form modenite that silica alumina ratio is 10 with silica alumina ratio, according to embodiment 1
Method carry out ion exchange, mix with boehmite (modenite/ZSM-5 zeolite/quality of alumina ratio=15:35:
50), carrying out extruded moulding, roasting, dipping, roasting and reduction according to the method for embodiment 1, obtain platinum content 0.08wt%, bismuth contains
The catalyst A5 of amount 1.0wt%.
Embodiment 6
It is after 150 sodium form ZSM-5 zeolites mix by sodium form modenite that silica alumina ratio is 10 with silica alumina ratio, according to embodiment
The method of 1 carries out ion exchange, mix with boehmite (modenite/ZSM-5 zeolite/quality of alumina ratio=15:35:
50), carrying out extruded moulding, roasting, dipping, roasting and reduction according to the method for embodiment 1, obtain platinum content 0.1wt%, bismuth contains
The catalyst A6 of amount 1.5wt%.
Embodiment 7
It is after 30 sodium form ZSM-5 zeolites mix by sodium form modenite that silica alumina ratio is 10 with silica alumina ratio, according to embodiment 1
Method carry out ion exchange, mix (modenite/ZSM-5 zeolite/quality of alumina ratio=5:65:30) with boehmite,
Carry out extruded moulding, roasting, dipping, roasting and reduction according to the method for embodiment 1, obtain platinum content 0.5wt%, bi content
The catalyst A7 of 0.1wt%.
Embodiment 8
It is after 150 sodium form ZSM-5 zeolites mix by sodium form modenite that silica alumina ratio is 10 with silica alumina ratio, according to embodiment
The method of 1 carries out ion exchange, mix with boehmite (modenite/ZSM-5 zeolite/quality of alumina ratio=5:65:
30), carrying out extruded moulding, roasting, dipping, roasting and reduction according to the method for embodiment 1, obtain platinum content 0.5wt%, bismuth contains
The catalyst A8 of amount 0.1wt%.
Embodiment 9
It is after 3 sodium form ZSM-5 zeolites mix by sodium form modenite that silica alumina ratio is 10 with silica alumina ratio, according to embodiment 1
Method carry out ion exchange, mix with boehmite (modenite/ZSM-5 zeolite/quality of alumina ratio=25:25:
50), carry out extruded moulding and roasting process according to the method for embodiment 1, in dipping process, catalyst base is immersed in and contains
Have in the solution of hydrochloric acid, chloroplatinic acid and Butter of antimony., carry out roasting and reduction process according to the method for embodiment 1, obtain platinum and contain
The catalyst A9 of amount 0.5wt%, antimony content 0.1wt%.
Embodiment 10
It is after 150 sodium form ZSM-5 zeolites mix by sodium form modenite that silica alumina ratio is 10 with silica alumina ratio, according to embodiment
The method of 1 carries out ion exchange, extruded moulding and roasting process, in dipping process, is immersed in catalyst base containing salt
In the solution of acid, dichloride four ammino palladium and bismuth chloride, the method according still further to embodiment 2 carries out roasting and reduction process, obtains
Palladium content 0.5wt%, bi content 0.1wt% catalyst A10.
Embodiment 11
It is after 150 sodium form ZSM-5 zeolites mix by sodium form modenite that silica alumina ratio is 10 with silica alumina ratio, according to embodiment
The method of 1 carries out ion exchange, extruded moulding and roasting process, in dipping process, is immersed in catalyst base containing salt
In the solution of acid, nickel nitrate and bismuth chloride, the method according still further to embodiment 2 carries out roasting and reduction process, obtains nickel content
0.5wt%, bi content 0.1wt% catalyst A11.
Comparative example 1
According to the method for embodiment 24 in patent application CN1443736A, by ammonium type modenite that silica alumina ratio is 10 and plan
Boehmite, by weight 70/30 mixing, adds dust technology and water, mediates uniformly, extrusion, 110 DEG C of drying, and pelletizing impregnates molybdic acid
Aqueous ammonium and cobalt nitrate aqueous solution, 110 DEG C of drying, 550 DEG C of roastings obtain metal molybdenum and metallic cobalt content be respectively 4.0w% and
The catalyst B1 of 0.6w%.
Comparative example 2
According to the method for embodiment 26 in patent application CN1443737A, by ammonium type modenite that silica alumina ratio is 10 and plan
Boehmite, by weight 70/30 mixing, adds dust technology and water, mediates uniformly, extrusion, 110 DEG C of drying, and pelletizing impregnates molybdic acid
Aqueous ammonium and chromium nitrate aqueous solution, 110 DEG C of drying, 550 DEG C of roastings obtain metal molybdenum and crome metal content be respectively 4.0w% and
The catalyst B2 of 1.1w%.
Embodiment 12
By catalyst A1-A11, B1, B2, it is contained on 100ml fixed bed evaluating apparatus, evaluates activity and the selection of catalyst
Property.Loaded catalyst 15g, reaction temperature 370 DEG C, reaction pressure 2.5MPa, hydrogen hydrocarbon mol ratio 4.0, weight (hourly) space velocity (WHSV) 4.0h-1,
Reaction raw materials forms such as table 1:
Table 1 evaluating catalyst raw material
| Composition | NA | B | T | C8A | C9 +A |
| Content/wt% | 0.06 | 41.50 | 0.02 | 1.0 | 57.42 |
Reaction evaluating the results are shown in Table 2.From table 2 it can be seen that when processing the raw material of benzene and carbon nine and above aromatic hydrocarbons, this
Bright described catalyst has higher catalysis activity and selectivity.
Table 2 evaluating catalyst result
| Catalyst is numbered | Bc/wt% | HAc/wt% | Yc/wt% |
| A1 | 46.5 | 73.7 | 93.6 |
| A2 | 48.6 | 75.3 | 93.1 |
| A3 | 44.5 | 73.1 | 93.0 |
| A4 | 43.8 | 74.9 | 93.5 |
| A5 | 47.3 | 73.5 | 94.2 |
| A6 | 46.9 | 74.1 | 93.9 |
| A7 | 48.0 | 75.2 | 92.8 |
| A8 | 48.2 | 76.7 | 92.4 |
| A9 | 45.9 | 72.8 | 93.3 |
| A10 | 47.4 | 73.2 | 92.7 |
| A11 | 33.8 | 55.3 | 91.6 |
| B1 | 39.1 | 70.2 | 90.5 |
| B2 | 45.2 | 72.6 | 86.7 |
Embodiment 13
By catalyst A1-A11, B1, B2, according to the appreciation condition of embodiment 9, raw material uses benzene and C9 aromatic to carry out instead
Should, raw material forms with evaluation result as shown in Table 3 and Table 4, C therein9Ac represents the conversion ratio of C9 aromatic.
Table 3 evaluating catalyst raw material
| Composition | NA | B | T | C8A | C9A |
| Content/wt% | 0.08 | 39.86 | 0.02 | 0.11 | 59.93 |
Table 4 evaluating catalyst result
| Catalyst is numbered | Bc/wt% | C9Ac/wt% | Yc/wt% |
| A1 | 47.5 | 74.3 | 93.9 |
| A2 | 49.0 | 75.7 | 94.1 |
| A3 | 44.9 | 73.5 | 93.3 |
| A4 | 43.7 | 74.8 | 93.7 |
| A5 | 47.6 | 74.2 | 94.4 |
| A6 | 47.3 | 73.9 | 94.3 |
| A7 | 48.8 | 76.9 | 93.0 |
| A8 | 48.9 | 77.4 | 92.8 |
| A9 | 45.3 | 72.2 | 93.8 |
| A10 | 47.4 | 74.9 | 93.9 |
| A11 | 38.4 | 67.9 | 91.7 |
| B1 | 41.2 | 71.7 | 90.8 |
| B2 | 47.2 | 73.2 | 88.3 |
Evaluation result shows, catalyst of the present invention is when processing the raw material of benzene and C9 aromatic, with catalyst treatment
Benzene is compared with the raw material of carbon nine and above aromatic hydrocarbons, and its catalysis activity and selectivity is more preferable.
Embodiment 14
By catalyst A1, A2, A7, A8, according to the appreciation condition of embodiment 9, reaction temperature is improved to 378 DEG C, raw material
Use benzene and carbon ten and above aromatic hydrocarbons (C10 +A) reacting, raw material forms with evaluation result as shown in table 5 and table 6, wherein C10 +
Ac represents carbon ten and the conversion ratio of above aromatic hydrocarbons.
Table 5 evaluating catalyst raw material
| Composition | NA | B | T | C8A and C9A | C10 +A |
| Content/wt% | 0.04 | 40.05 | 0.08 | 0.23 | 59.60 |
Table 6 evaluating catalyst result
| Catalyst is numbered | Bc/wt% | C10 +Ac/wt% | Yc/wt% |
| A1 | 43.8 | 70.6 | 90.2 |
| A2 | 44.2 | 71.1 | 89.1 |
| A7 | 46.6 | 73.2 | 88.5 |
| A8 | 47.1 | 73.8 | 87.9 |
Evaluation result shows, the catalyst of the present invention is processing benzene and heavier carbon ten and the mixing raw material of above aromatic hydrocarbons
Time, still there is higher catalysis activity and selectivity.
Claims (10)
1. one kind with benzene and heavy aromatics for raw material production toluene and the application of the catalyst of C8 aronmatic, it is characterised in that: with benzene
It is raw material with heavy aromatics, in the presence of described catalyst, in reaction temperature 300-500 DEG C, hydrogen partial pressure 1.0-3.5MPa, charging
Air speed 0.25-30h-1, under conditions of hydrogen hydrocarbon mol ratio 3.0-5.0, produce toluene and C8 aronmatic；
Count with catalyst weight for 100wt%, described catalyst by 1-25wt%MOR zeolite, 1-65wt%ZSM-5 zeolite,
At least one periodic table of elements the Vth A race element, at least one periodic table of elements of 0.01-2.0wt% of 0.01-3.0wt%
The binding agent composition of the VIIIth race's element and surplus；Wherein, described MOR zeolite and ZSM-5 zeolite all contain silicon and aluminum, and total
Si/Al atomic ratio is more than 5；Described Vth A race metal is selected from antimony and bismuth；Described group VIII metal is selected from platinum and palladium；
Described raw material is selected from: benzene and the mixture of C9 aromatic, benzene and carbon nine and the mixture of above aromatic hydrocarbons or benzene and carbon ten and
The mixture of above aromatic hydrocarbons.
2. described in claim 1 with benzene and heavy aromatics for raw material production toluene and the application of the catalyst of C8 aronmatic, it is special
Levy and be: described reaction temperature is in the range of 320-450 DEG C；Described hydrogen partial pressure is in the range of 1.5-3.0MPa；Described
Feed space velocities is at 1-10h-1In the range of.
3. described in claim 2 with benzene and heavy aromatics for raw material production toluene and the application of the catalyst of C8 aronmatic, it is special
Levy and be: described reaction temperature is in the range of 340-430 DEG C；Described hydrogen partial pressure is in the range of 2.0-2.8MPa；Described
Feed space velocities is at 2-6h-1In the range of.
4. described in claim 3 with benzene and heavy aromatics for raw material production toluene and the application of the catalyst of C8 aronmatic, it is special
Levy and be: described MOR zeolite and ZSM-5 zeolite are H+The zeolite of type, described MOR zeolite and the Si/Al atom of ZSM-5 zeolite
Than for more than 5 and less than or equal to 300；Sodium content in described zeolite is that Na/Al atomic ratio is less than 0.02.
5. according to described in claim 4 with benzene and heavy aromatics for raw material production toluene and the application of the catalyst of C8 aronmatic,
It is characterized in that: count with catalyst weight for 100wt%, the content of described Vth A race metal is 0.08-1.5wt%；Described
The content of VIII race's metal is 0.08-1.5wt%.
6. according to described in claim 5 with benzene and heavy aromatics for raw material production toluene and the application of the catalyst of C8 aronmatic,
It is characterized in that: described binding agent is the mixture being made up of aluminium oxide and clay.
7. according to described in claim 6 with benzene and heavy aromatics for raw material production toluene and the application of the catalyst of C8 aronmatic,
It is characterized in that: the preparation of described catalyst comprises the steps:
(1) MOR zeolite and ZSM-5 zeolite carrying out pretreatment, the organic formwork agent in removing zeolite micropore, then with at least one
Plant ammonium salt solution and carry out ion-exchange step at least one times, to remove the alkali metal cation in zeolite；
(2) by the zeolite mixed-forming after binding agent and above-mentioned process, it is prepared as extrudate or spherical；
(3) it is dried at a temperature of ambient temperature to 250 DEG C, then in air or oxygen, enters at a temperature of 250-600 DEG C
Row roasting；
(4) at least one the Vth A race element and at least one the VIIIth race's element are deposited；
(5) in air or oxygen, roasting 0.5-10 hour at 250-600 DEG C, then in the atmosphere of hydrogen, at 300-
Reduce 1-10 hour at 600 DEG C, it is thus achieved that reduction-state catalyst.
8. according to described in claim 7 with benzene and heavy aromatics for raw material production toluene and the application of the catalyst of C8 aronmatic,
It is characterized in that: the deposition of at least one group VIII metal element is carried out with the method for dry leaching, excess dipping or ion exchange, makes
By platinum and/or palladium salt, add hydrochloric acid while deposition as competitive adsorbate；Described platinum salt is selected from chloroplatinic acid, dichloro four ammino
One or more in platinum, tetrachloro six ammino platinum or tetrachloro two ammino platinum；Described palladium salt is selected from Palladous nitrate., dinitro four ammino
Palladium, palladium chloride, dichloride four ammino palladium or diamminodichloro close one or more in palladium.
9. according to described in claim 8 with benzene and heavy aromatics for raw material production toluene and the application of the catalyst of C8 aronmatic,
It is characterized in that: the deposition of at least one the Vth A race metallic element deposits in the way of dry leaching, excess dipping or ion exchange,
Introduced by the chloride of the Vth A race metallic element, bromide, sulfate or nitrate；Vth A race metallic element is in the VIIIth race
Before metallic element, introduce simultaneously or after.
10. according to described in claim 9 with benzene and heavy aromatics for raw material production toluene and the application of the catalyst of C8 aronmatic,
It is characterized in that: after described metallic element deposition, in the atmosphere of air or oxygen, roasting 1-4 at a temperature of 350-550 DEG C
Hour, then in the atmosphere of hydrogen, reductase 12-5 hours at a temperature of 350-550 DEG C, it is thus achieved that reduction-state catalyst.
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