CN109395715A - Heavy arene efficient hydrogenation catalyst - Google Patents
Heavy arene efficient hydrogenation catalyst Download PDFInfo
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- CN109395715A CN109395715A CN201710709585.8A CN201710709585A CN109395715A CN 109395715 A CN109395715 A CN 109395715A CN 201710709585 A CN201710709585 A CN 201710709585A CN 109395715 A CN109395715 A CN 109395715A
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- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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Abstract
The present invention relates to a kind of heavy arene efficient hydrogenation catalyst, mainly solve to exist in the prior art that condensed-nuclei aromatics hydrogenation activity is not high, the selectively relatively low problem of mononuclear aromatics.The present invention passes through a kind of heavy aromatics efficient hydrogenation catalyst, including the porous carrier modified containing compound L acid assistant, and the technical solution of at least two hydrogenation metal elements or compound selected from VIII race of load thereon, significantly improve condensed-nuclei aromatics hydrogenation activity and mononuclear aromatics selectivity.
Description
Technical field
The present invention relates to a kind of heavy arene efficient hydrogenation catalysts and preparation method thereof.
Background technique
Condensed-nuclei aromatics refers to bicyclic and multiring structure aromatic component, be largely present in catalytic cracking, ethylene bottom oil and
The processes such as paraxylene production, it is most of to be reconciled as diesel oil if catalytic cracking light cycle oil annual output is more than 10,000,000
Component.Recently as the continuous increase of China's PX demand, PX is presented the situation that supply falls short of demand, realizes the big of Aromatic Hydrocarbon United Plant
Type and raw material diversification are to solve the problems, such as one of the key factor of current paraxylene industrial production.Therefore, virtue is made full use of
Hydrocarbon combined unit by-product condensed-nuclei aromatics, research and utilization oil refining apparatus by-product condensed-nuclei aromatics produce light aromatics with important meaning
Justice.From the point of view of reaction process, realize conversion most critical from condensed-nuclei aromatics to mononuclear aromatics the step of be realization condensed-nuclei aromatics choosing
Selecting property adds hydrogen, and polycyclic aromatic hydrocarbon partial hydrogenation is generated mononuclear aromatics component.It coexists in system, realizes more in monocycle and polycyclic aromatic hydrocarbon
Cycloaromatics selective hydrogenation is the key that improve mononuclear aromatics yield.The metals quilt such as noble metal platinum, palladium and base metal molybdenum, nickel
Report adds hydrogen saturation for polycyclic aromatic hydrocarbon.
CN104117386A discloses a kind of condensed-nuclei aromatics and adds hydrogen ring opening catalyst, and catalyst is containing 5%-100%'s
Beta molecular sieve component, and the noble metal for selecting Pt, Ir, Pd of the 0.1%-3% of load thereon.
CN102688770A discloses a kind of aromatic hydrocarbon hydrogenation catalyst, is to form with mesoporous zeolite and noble metal, improves
The hydrogenation aromatics-removing activity and sulfur resistance of catalyst.
CN103301874B discloses the method and carbon monoxide-olefin polymeric of a kind of polycyclic aromatic hydrocarbon selective hydrogenation open loop, including
Acidic molecular sieve loads VIII family metal oxide and catalyst containing Mo, and catalyst containing Mo is Mo and the bimetallic of transition metal composition
Sulfide significantly improves the yield of selective opening product using combination catalyst and water additive.
CN103666553 discloses a kind of method of hydro-conversion polycyclic aromatic hydrocarbon, and polycyclic aromatic hydrocarbon is first in hydroconversion reaction zone
It is at least partially saturated, 40% or more polycyclic aromatic hydrocarbon conversion ratio of acquisition, mononuclear aromatics yield 4-80%,；Pass through hydrocracking again
Reaction zone reaction, obtains 85% or more polycyclic aromatic hydrocarbon conversion ratio, mononuclear aromatics yield advantage 4-30%, to reduce polycyclic aromatic hydrocarbon
Convert hydrogen consumption.
Above patent document is not directed to that monocycle, condensed-nuclei aromatics coexists under system, realizes condensed-nuclei aromatics highly effective hydrogenation
Generate the technology of mononuclear aromatics.
Summary of the invention
The technical problem to be solved by the present invention is to the prior arts there is a problem of that condensed-nuclei aromatics hydrogenation activity is low, provide one
Kind new condensed-nuclei aromatics selective hydrocatalyst when the catalyst is for handling material containing condensed-nuclei aromatics, has condensed-nuclei aromatics
The high advantage of hydrogenation activity.
In order to solve the above technical problems, the present invention is as follows using technical solution: a kind of heavy arene efficient hydrogenation catalyst,
It include: the porous carrier modified containing compound L acid assistant, and at least two hydrogenation metal elements selected from VIII race of load thereon
Or compound.
In above-mentioned technical proposal, the porous carrier is selected from aluminium oxide, silica, magnesia, amorphous silica-alumina, kaolinite
At least one of soil, alumino-silicate, the compound L acid assistant includes chloride ion compound and fluoride ion source simultaneously.
The chloride ion compound is selected from least one of AlCl3, CuCl2, FeCl3, SnCl4, TiCl4, SbCl5,
The fluoride ion source is selected from least one of BF3, NbF5, SbF5, TaF5, AsF5.The hydrogenation metal be selected from Pt,
At least one of Pd, Rh, Ir.
In more optimized scheme, the compound L acid assistant includes AlCl3 and NbF5 mixture simultaneously, wherein AlCl3 and NbF5
Weight ratio be (0.1~10): 1；The mixture of AlCl3 and NbF5 has collaboration in terms of improving fused ring compound hydrogenation activity
Effect.
In more optimized scheme, the hydrogenation metal includes the mixture of Pt and Pd simultaneously, and wherein the weight ratio of Pt and Pd is
(0.1~10): 1；The mixture of Pt and Pd has synergistic effect in terms of the selective hydrogenation for improving fused ring compound.
The heavy aromatics efficient hydrogenation catalyst, based on parts by weight, compound L acid assistant content are overall catalyst weight
0.01-20 parts, prioritization scheme is 0.05-15 parts.Based on parts by weight, hydrogenation metal content is the 0.01-5 of overall catalyst weight
Part, prioritization scheme is 0.02-3 parts.
To solve above-mentioned technical problem two, the present invention is as follows using technical solution: a kind of heavy aromatics highly effective hydrogenation catalysis
The preparation method of agent, comprising:
First the L acid assistant is previously bound in porous carrier presoma by chemically or physically method or by the L
Acid assistant is integrated to porous carrier surface and obtains L acid assistant modified support by dipping, precipitating, adsorption method.Described it will add again
Hydrometallation closes object and is integrated to the modified porous carrier surface of acid assistant containing L by way of dipping, absorption, precipitating, obtains weight
Aromatic hydrocarbons efficient hydrogenation catalyst.
The catalyst is 100-500 DEG C, reaction pressure 1.0-5MPa in reaction temperature, and hydrogen hydrocarbon molar ratio is 1-8, into
Material weight space velocity is reacted under the conditions of being 0.5-20.
In the present invention, the modified porous carrier of L acid assistant can provide more active acid sites, improve condensed-nuclei aromatics conversion
Frequency.Hydrogen is dissociated on hydrogenation metal position under the cited reaction conditions to migrate, and further promote to be adsorbed on the acid site L
Condensed-nuclei aromatics hydrogenation reaction.Therefore catalyst shows higher condensed-nuclei aromatics hydrogenation activity.The catalyst treatment is containing condensed ring virtue
When hydrocarbon material, there is the advantages of condensed-nuclei aromatics hydrogenation activity is high, mononuclear aromatics high income.
Below by the description to embodiment, further illustrates but does not limit the present invention:
Specific embodiment
[embodiment 1]
Take 20 grams of alumina balls carriers, a certain amount of aluminum trichloride solution of incipient impregnation, 120 DEG C drying 4 hours, 550
DEG C roasting 4 hours, be made alchlor content be 5% (wt) L acid modified catalyst A1, by catalyst A1 incipient impregnation one
Determine chloroplatinic acid and palladium chloride solution, obtains the catalyst B1 that platinum content is 0.1% (wt), palladium content is 0.2% (wt).
5 grams of catalyst B1 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, is passed through
Hydrogen and containing toluene and naphthalene material are contacted with catalyst carries out reactivity investigation.Reaction condition are as follows: total weight air speed is
10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are hexadecane: naphthalene=40:60
(weight), reactivity worth is as shown in table 1, and mononuclear aromatics selectively refers to the ratio between mononuclear aromatics amount and the amount of naphthalene of conversion in product.
[embodiment 2]
Take 20 grams of alumina balls carriers, a certain amount of cupric chloride solution of incipient impregnation, 120 DEG C drying 4 hours, 550
DEG C roasting 4 hours, be made dichloride copper content be 5% (wt) L acid modified catalyst A2, by catalyst A2 incipient impregnation one
Determine chloroplatinic acid and palladium chloride solution, obtains the catalyst B2 that platinum content is 0.1% (wt), palladium content is 0.2% (wt).
5 grams of catalyst B2 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, is passed through
Hydrogen and containing toluene and naphthalene material are contacted with catalyst carries out reactivity investigation.Reaction condition are as follows: total weight air speed is
10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are hexadecane: naphthalene=40:60
(weight), reactivity worth is as shown in table 1.
[embodiment 3]
Take 20 grams of alumina balls carriers, a certain amount of liquor ferri trichloridi of incipient impregnation, 120 DEG C drying 4 hours, 550
DEG C roasting 4 hours, be made ferric trichloride content be 5% (wt) L acid modified catalyst A3, by catalyst A3 incipient impregnation one
Determine chloroplatinic acid and palladium chloride solution, obtains the catalyst B3 that platinum content is 0.1% (wt), palladium content is 0.2% (wt).
5 grams of catalyst B3 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, is passed through
Hydrogen and containing toluene and naphthalene material are contacted with catalyst carries out reactivity investigation.Reaction condition are as follows: total weight air speed is
10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are hexadecane: naphthalene=40:60
(weight), reactivity worth is as shown in table 1.
[embodiment 4]
Take 20 grams of alumina balls carriers, a certain amount of tin tetrachloride solution of incipient impregnation, 120 DEG C drying 4 hours, 550
DEG C roasting 4 hours, be made tin tetrachloride content be 5% (wt) L acid modified catalyst A4, by catalyst A4 incipient impregnation one
Determine chloroplatinic acid and palladium chloride solution, obtains the catalyst B4 that platinum content is 0.1% (wt), palladium content is 0.2% (wt).
5 grams of catalyst B4 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, is passed through
Hydrogen and containing toluene and naphthalene material are contacted with catalyst carries out reactivity investigation.Reaction condition are as follows: total weight air speed is
10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are hexadecane: naphthalene=40:60
(weight), reactivity worth is as shown in table 1.
[embodiment 5]
Take 20 grams of alumina balls carriers, a certain amount of boron trifluoride solution of incipient impregnation, 120 DEG C drying 4 hours, 550
DEG C roasting 4 hours, be made boron trifluoride content be 5% (wt) L acid modified catalyst A5, by catalyst A5 incipient impregnation one
Determine chloroplatinic acid and palladium chloride solution, obtains the catalyst B5 that platinum content is 0.1% (wt), palladium content is 0.2% (wt).
5 grams of catalyst B5 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, is passed through
Hydrogen and containing toluene and naphthalene material are contacted with catalyst carries out reactivity investigation.Reaction condition are as follows: total weight air speed is
10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are hexadecane: naphthalene=40:60
(weight), reactivity worth is as shown in table 1.
[embodiment 6]
Take 20 grams of alumina balls carriers, a certain amount of SbF5 solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings
It burns 4 hours, the L acid modified catalyst A6 that SbF5 content is 5% (wt) is made, by the certain chloroplatinic acid of catalyst A6 incipient impregnation
And palladium chloride solution, obtain the catalyst B6 that platinum content is 0.1% (wt), palladium content is 0.2% (wt).
5 grams of catalyst B6 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, is passed through
Hydrogen and containing toluene and naphthalene material are contacted with catalyst carries out reactivity investigation.Reaction condition are as follows: total weight air speed is
10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are hexadecane: naphthalene=40:60
(weight), reactivity worth is as shown in table 1.
[embodiment 7]
Take 20 grams of alumina balls carriers, a certain amount of AsF5 solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings
It burns 4 hours, the L acid modified catalyst A7 that AsF5 content is 5% (wt) is made, by the certain chloroplatinic acid of catalyst A7 incipient impregnation
And palladium chloride solution, obtain the catalyst B7 that platinum content is 0.1% (wt), palladium content is 0.2% (wt).
5 grams of catalyst B7 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, is passed through
Hydrogen and containing toluene and naphthalene material are contacted with catalyst carries out reactivity investigation.Reaction condition are as follows: total weight air speed is
10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are dodecane: naphthalene=40:60
(weight), reactivity worth is as shown in table 1.
[embodiment 8]
Take 20 grams of alumina balls carriers, a certain amount of NbF5 solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings
It burns 4 hours, the L acid modified catalyst A8 that NbF5 content is 5% (wt) is made, by the certain chloroplatinic acid of catalyst A8 incipient impregnation
And palladium chloride solution, obtain the catalyst B8 that platinum content is 0.1% (wt), palladium content is 0.2% (wt).
5 grams of catalyst B8 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, is passed through
Hydrogen and containing toluene and naphthalene material are contacted with catalyst carries out reactivity investigation.Reaction condition are as follows: total weight air speed is
10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are dodecane: naphthalene=40:60
(weight), reactivity worth is as shown in table 1.
[embodiment 9]
Take 20 grams of balloon borne bodies of magnesia, a certain amount of AlCl3 and BF3 solution of incipient impregnation, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, and the L acid modified catalyst A9 that AlCl3 content is 2% (wt), BF3 content is 3% (wt) is made, will urge
The certain chloroplatinic acid of agent A9 incipient impregnation and palladium chloride solution, obtain that platinum content is 0.1% (wt), palladium content is 0.2% (wt)
Catalyst B9.
5 grams of catalyst B9 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, is passed through
Hydrogen and containing toluene and naphthalene material are contacted with catalyst carries out reactivity investigation.Reaction condition are as follows: total weight air speed is
10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are dodecane: naphthalene=40:60
(weight), reactivity worth is as shown in table 1.
[embodiment 10]
Take the shaping carrier of 20 grams of Beta molecular sieves and aluminium oxide, a certain amount of AlCl3 and SbF5 solution of incipient impregnation,
120 DEG C drying 4 hours, 550 DEG C roast 4 hours, and AlCl3 content is 2% (wt), SbF5 content is 3% (wt) L acid is made and changes
Property catalyst A10, by the certain chloroplatinic acid of catalyst A10 incipient impregnation and palladium chloride solution, obtain platinum content be 0.1% (wt),
Palladium content is the catalyst B10 of 0.2% (wt).
5 grams of catalyst B10 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, leads to
Enter hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total weight air speed
It is 10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are dodecane: naphthalene=40:
60 (weight), reactivity worth is as shown in table 1.
[embodiment 11]
Take 20 grams of alumina balls carriers, a certain amount of AlCl3 and NbF5 solution of incipient impregnation, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, and the L acid modified catalyst A11 that AlCl3 content is 2% (wt), NbF5 content is 3% (wt) is made, will
The certain chloroplatinic acid of catalyst A11 incipient impregnation and palladium chloride solution, obtaining platinum content is 0.1% (wt), palladium content 0.2%
(wt) catalyst B11.
5 grams of catalyst B11 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, leads to
Enter hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total weight air speed
It is 10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are dodecane: naphthalene=40:
60 (weight), reactivity worth is as shown in table 1.
[embodiment 12]
Take 20 grams of alumina balls carriers, a certain amount of CuCl3 and NbF5 solution of incipient impregnation, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, and the L acid modified catalyst A12 that CuCl3 content is 2% (wt), NbF5 content is 3% (wt) is made, will
The certain chloroplatinic acid of catalyst A12 incipient impregnation and palladium chloride solution, obtaining platinum content is 0.1% (wt), palladium content 0.2%
(wt) catalyst B12.
5 grams of catalyst B12 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, leads to
Enter hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total weight air speed
It is 10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are dodecane: naphthalene=40:
60 (weight), reactivity worth is as shown in table 1.
[embodiment 13]
Take 20 grams of alumina balls carriers, a certain amount of FeCl3 and NbF5 solution of incipient impregnation, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, and the L acid modified catalyst A13 that FeCl3 content is 2% (wt), NbF5 content is 3% (wt) is made, will
The certain chloroplatinic acid of catalyst A13 incipient impregnation and palladium chloride solution, obtaining platinum content is 0.1% (wt), palladium content 0.2%
(wt) catalyst B13.
5 grams of catalyst B13 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, leads to
Enter hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total weight air speed
It is 10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are dodecane: naphthalene=40:
60 (weight), reactivity worth is as shown in table 1.
[embodiment 14]
Take 20 grams of alumina balls carriers, a certain amount of AlCl3 and NbF5 solution of incipient impregnation, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, and the L acid modified catalyst A14 that AlCl3 content is 2% (wt), NbF5 content is 3% (wt) is made, will
The certain chloroplatinic acid of catalyst A14 incipient impregnation and rhodium chloride solution, obtaining platinum content is 0.1% (wt), rhodium content 0.2%
(wt) catalyst B14.
5 grams of catalyst B14 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, leads to
Enter hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total weight air speed
It is 10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are dodecane: naphthalene=40:
60 (weight), reactivity worth is as shown in table 1.
[embodiment 15]
Take 20 grams of alumina balls carriers, a certain amount of AlCl3 and NbF5 solution of incipient impregnation, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, and the L acid modified catalyst A15 that AlCl3 content is 2% (wt), NbF5 content is 3% (wt) is made, will
The certain chloroplatinic acid of catalyst A15 incipient impregnation and Chloroiridic Acid solution, obtain that platinum content is 0.1% (wt), iridium content is 0.2%
(wt) catalyst B15.
5 grams of catalyst B15 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, leads to
Enter hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total weight air speed
It is 10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are dodecane: naphthalene=40:
60 (weight), reactivity worth is as shown in table 1.
[embodiment 16]
Take 20 grams of alumina balls carriers, a certain amount of AlCl3 and NbF5 solution of incipient impregnation, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, and the L acid modified catalyst A16 that AlCl3 content is 1% (wt), NbF5 content is 4% (wt) is made, will
The certain chloroplatinic acid of catalyst A16 incipient impregnation and palladium chloride solution, obtaining platinum content is 0.1% (wt), palladium content 0.2%
(wt) catalyst B16.
5 grams of catalyst B16 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, leads to
Enter hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total weight air speed
It is 10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are dodecane: naphthalene=40:
60 (weight), reactivity worth is as shown in table 1.
[embodiment 17]
Take 20 grams of alumina balls carriers, a certain amount of AlCl3 and NbF5 solution of incipient impregnation, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, and the L acid modified catalyst A17 that AlCl3 content is 4% (wt), NbF5 content is 1% (wt) is made, will
The certain chloroplatinic acid of catalyst A17 incipient impregnation and palladium chloride solution, obtaining platinum content is 0.1% (wt), palladium content 0.2%
(wt) catalyst B17.
5 grams of catalyst B17 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, leads to
Enter hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total weight air speed
It is 10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are dodecane: naphthalene=40:
60 (weight), reactivity worth is as shown in table 1.
[embodiment 18]
Take 20 grams of alumina balls carriers, a certain amount of AlCl3 and NbF5 solution of incipient impregnation, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, and the L acid modified catalyst A18 that AlCl3 content is 2% (wt), NbF5 content is 3% (wt) is made, will
The certain chloroplatinic acid of catalyst A18 incipient impregnation and palladium chloride solution, obtaining platinum content is 0.25% (wt), palladium content 0.05%
(wt) catalyst B18.
5 grams of catalyst B18 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, leads to
Enter hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total weight air speed
It is 10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are dodecane: naphthalene=40:
60 (weight), reactivity worth is as shown in table 1.
[embodiment 19]
Take 20 grams of alumina balls carriers, a certain amount of AlCl3 and NbF5 solution of incipient impregnation, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, and the L acid modified catalyst A19 that AlCl3 content is 2% (wt), NbF5 content is 3% (wt) is made, will
The certain chloroplatinic acid of catalyst A19 incipient impregnation and palladium chloride solution, obtaining platinum content is 0.05% (wt), palladium content 0.25%
(wt) catalyst B19.
5 grams of catalyst B19 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, leads to
Enter hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total weight air speed
It is 10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are dodecane: naphthalene=40:
60 (weight), reactivity worth is as shown in table 1.
[comparative example 1]
Take 20 grams of alumina balls carriers, a certain amount of AlCl3 and NbF5 solution of incipient impregnation, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, and the L acid modified catalyst A20 that AlCl3 content is 2% (wt), NbF5 content is 3% (wt) is made, will
The certain chloroplatinic acid of catalyst A20 incipient impregnation obtains the catalyst B20 that platinum content is 0.3% (wt).
5 grams of catalyst B20 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, leads to
Enter hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total weight air speed
It is 10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are dodecane: naphthalene=40:
60 (weight), reactivity worth is as shown in table 1.
[comparative example 2]
20 grams of alumina balls carriers, the certain chloroplatinic acid of incipient impregnation and palladium chloride solution are taken, obtaining platinum content is 0.1%
(wt), palladium content is the catalyst B21 of 0.2% (wt).
5 grams of catalyst B21 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, leads to
Enter hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total weight air speed
It is 10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are dodecane: naphthalene=40:
60 (weight), reactivity worth is as shown in table 1.
[comparative example 3]
Take 20 grams of alumina balls carriers, a certain amount of AlCl3 solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings
It burns 4 hours, the L acid modified catalyst A22 that AlCl3 content is 5% (wt) is made.
5 grams of catalyst A22 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, leads to
Enter hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total weight air speed
It is 10 hours-1, 350 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0.Reaction raw materials are dodecane: naphthalene=40:
60 (weight), reactivity worth is as shown in table 1.
Table 1
Claims (10)
1. a kind of heavy arene efficient hydrogenation catalyst, comprising:
A) porous carrier modified containing compound L acid assistant, and load thereon
B) at least two hydrogenation metal element or compound selected from VIII race.
2. heavy arene efficient hydrogenation catalyst according to claim 1, it is characterised in that the porous carrier is selected from oxygen
Change at least one of aluminium, silica, magnesia, amorphous silica-alumina, kaolin, alumino-silicate.
3. heavy arene efficient hydrogenation catalyst according to claim 1, it is characterised in that the compound L acid assistant is simultaneously
Including chloride ion compound and fluoride ion source.
4. according to claim 1, heavy arene efficient hydrogenation catalyst described in 3, it is characterised in that the chloride ion compound
Selected from least one of AlCl3, CuCl2, FeCl3, SnCl4, TiCl4, SbCl5.
5. according to claim 1, heavy arene efficient hydrogenation catalyst described in 3, it is characterised in that the fluoride ion source
Selected from least one of BF3, NbF5, SbF5, TaF5, AsF5.
6. heavy arene efficient hydrogenation catalyst according to claim 1, it is characterised in that the hydrogenation metal be selected from Pt,
At least one of Pd, Rh, Ir.
7. heavy arene efficient hydrogenation catalyst according to claim 1, which is characterized in that based on parts by weight, compound L
Acid assistant content is 0.01-20 part of overall catalyst weight；Based on parts by weight, hydrogenation metal content is overall catalyst weight
0.01-5 parts.
8. a kind of preparation method using any one heavy arene efficient hydrogenation catalyst described in claim 1~7, special
Sign is that the L acid assistant is previously bound in porous carrier presoma by chemically or physically method.
9. a kind of preparation method using any one heavy arene efficient hydrogenation catalyst described in claim 1~8, special
Sign is that the L acid assistant is integrated to porous carrier surface by dipping, precipitating, adsorption method；The hydrogenation metal passes through leaching
Stain, absorption, precipitating mode be integrated to the modified porous carrier surface of acid assistant containing L.
10. a kind of heavy arene highly effective hydrogenation reaction method, high using any one heavy arene described in claim 1~9
Imitate hydrogenation catalyst, which is characterized in that reaction temperature is 100-500 DEG C, reaction pressure 1.0-5MPa, and hydrogen hydrocarbon molar ratio is 1-
8, feed weight air speed is 0.5-20.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710709585.8A CN109395715B (en) | 2017-08-18 | 2017-08-18 | High-efficiency hydrogenation catalyst for heavy aromatic hydrocarbon |
| JP2018153138A JP7158953B2 (en) | 2017-08-18 | 2018-08-16 | Catalyst for producing light aromatic hydrocarbons from heavy aromatic hydrocarbons, production method and application thereof |
| KR1020180095695A KR102504661B1 (en) | 2017-08-18 | 2018-08-16 | Catalyst for producing light aromatics with heavy aromatics, method for preparing the catalyst, and use thereof |
| DE102018213896.6A DE102018213896A1 (en) | 2017-08-18 | 2018-08-17 | Catalyst for the production of light aromatic substances with heavy aromatic substances, process for the preparation of the catalyst and use thereof |
| ES201830831A ES2700899B2 (en) | 2017-08-18 | 2018-08-17 | Catalyst for producing light aromatics with heavy aromatics, method of preparing the catalyst and use thereof |
| BE2018/5572A BE1025972B1 (en) | 2017-08-18 | 2018-08-17 | CATALYST FOR PRODUCING LIGHT AROMATICS WITH HEAVY AROMATICS, PROCESS FOR PREPARING THE CATALYST AND USE THEREOF |
| US16/105,293 US11065604B2 (en) | 2017-08-18 | 2018-08-20 | Catalyst for producing light aromatics with heavy aromatics, method for preparing the catalyst, and use thereof |
| FR1800885A FR3070130B1 (en) | 2017-08-18 | 2018-08-20 | CATALYST FOR PRODUCING LIGHT AROMATICS WITH HEAVY AROMATICS, METHOD FOR PREPARING THE CATALYST AND USE THEREOF |
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|---|---|---|---|---|
| US3017369A (en) * | 1959-04-02 | 1962-01-16 | Universal Oil Prod Co | Catalyst manufacturing with control of halogen |
| US3524808A (en) * | 1967-02-21 | 1970-08-18 | Shell Oil Co | Hydrocracking catalyst containing carrier treated with a solution of nh4f in hno3 |
| CN1245088A (en) * | 1998-08-18 | 2000-02-23 | 中国石油化工集团公司 | Catalyst containng crystal silicoaluminate zeolite and noble metal and its preparing process |
| CN103121895A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing monocyclic aromatic hydrocarbons by polycyclic aromatic hydrocarbons |
| CN106588533A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Method for increasing yield of xylene through lightening of heavy aromatic hydrocarbons |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3017369A (en) * | 1959-04-02 | 1962-01-16 | Universal Oil Prod Co | Catalyst manufacturing with control of halogen |
| US3524808A (en) * | 1967-02-21 | 1970-08-18 | Shell Oil Co | Hydrocracking catalyst containing carrier treated with a solution of nh4f in hno3 |
| CN1245088A (en) * | 1998-08-18 | 2000-02-23 | 中国石油化工集团公司 | Catalyst containng crystal silicoaluminate zeolite and noble metal and its preparing process |
| CN103121895A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing monocyclic aromatic hydrocarbons by polycyclic aromatic hydrocarbons |
| CN106588533A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Method for increasing yield of xylene through lightening of heavy aromatic hydrocarbons |
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