CN109395726A - Fused ring compound selective hydrocatalyst - Google Patents

Fused ring compound selective hydrocatalyst Download PDF

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Publication number
CN109395726A
CN109395726A CN201710709612.1A CN201710709612A CN109395726A CN 109395726 A CN109395726 A CN 109395726A CN 201710709612 A CN201710709612 A CN 201710709612A CN 109395726 A CN109395726 A CN 109395726A
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compound
catalyst
fused ring
hours
ring compound
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CN109395726B (en
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孔德金
李经球
陈雪梅
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Priority to CN201710709612.1A priority Critical patent/CN109395726B/en
Priority to JP2018153138A priority patent/JP7158953B2/en
Priority to KR1020180095695A priority patent/KR102504661B1/en
Priority to ES201830831A priority patent/ES2700899B2/en
Priority to DE102018213896.6A priority patent/DE102018213896A1/en
Priority to BE2018/5572A priority patent/BE1025972B1/en
Priority to FR1800885A priority patent/FR3070130B1/en
Priority to US16/105,293 priority patent/US11065604B2/en
Publication of CN109395726A publication Critical patent/CN109395726A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/60—Platinum group metals with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • C10G45/52—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing platinum group metals or compounds thereof

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a kind of fused ring compound selective hydrocatalyst, mainly solve to exist in the prior art that fused ring compound hydrogenation selectivity is not high, the high problem of mononuclear aromatics loss late.The present invention passes through a kind of condensed-nuclei aromatics selective hydrocatalyst, it include: containing nonacid or faintly acid porous carrier, and at least two metallic elements or compound selected from VIII, I B, II B of load thereon, the metallic element or compound are in the technical solution of nuclear shell distribution on the surface of the carrier, significantly improve fused ring compound hydrogenation selectivity.

Description

Fused ring compound selective hydrocatalyst
Technical field
The present invention relates to a kind of fused ring compound selective hydrocatalysts 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 PX production, it is most of by as diesel oil blending component if catalytic cracking light cycle oil annual output is more than 10,000,000.Closely As the situation that supply falls short of demand is presented in the continuous increase of China's PX demand, PX over year, realize Aromatic Hydrocarbon United Plant enlargement and Raw material diversification is to solve the problems, such as one of the key factor of current PX industrial production.Therefore, Aromatic Hydrocarbon United Plant pair is made full use of Produce condensed-nuclei aromatics, the condensed-nuclei aromatics of research and utilization oil refining apparatus by-product is of great significance to produce light aromatics.From reacting From the point of view of journey, realize conversion most critical from condensed-nuclei aromatics to mononuclear aromatics the step of be realize condensed-nuclei aromatics selective hydrogenation, general Polycyclic aromatic hydrocarbon partial hydrogenation generates mononuclear aromatics component.It is coexisted in system in monocycle and polycyclic aromatic hydrocarbon, realizes that arenes selectivity adds Hydrogen is the significant process for improving mononuclear aromatics yield.The metals such as noble metal platinum, palladium and base metal molybdenum, nickel have been reported for more Cycloaromatics adds hydrogen saturation.
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 that condensed-nuclei aromatics is highly selective Partial hydrogenation technology.
Summary of the invention
The technical problem to be solved by the present invention is to the prior art, that there are condensed-nuclei aromatics hydrogenation selectivities is low, mononuclear aromatics damage Lose high problem, a kind of new condensed-nuclei aromatics selective hydrocatalyst be provided, the catalyst for handle containing mononuclear aromatics with When condensed-nuclei aromatics material, have condensed-nuclei aromatics selective hydrogenation rate high, mononuclear aromatics loses small advantage.
In order to solve the above technical problems, the present invention is as follows using technical solution: a kind of condensed-nuclei aromatics selective hydrogenation catalysis Agent include: containing nonacid or faintly acid porous carrier, and load thereon be selected from VIII, I in at least two of nuclear shell distribution B, the metallic element or compound of II B.
In above-mentioned technical proposal, nonacid or faintly acid porous carrier is selected from aluminium oxide, amorphous silica-alumina, kaolin, silicon At least one of aluminate.The nuclear phase layer metal is selected from least one of metal and its compound of Zn, Cu, Cd, Ag. In more excellent scheme, the nuclear phase layer metal simultaneously include Zn and Cu mixture, wherein the weight ratio of Zn and Cu be (0.1~ 10): 1.Zn and Cu has synergistic effect in terms of the selective hydrogenation activity for improving fused ring compound.
The shell phase layer metal is selected from least one of Pt, Pd, Ir metal and its compound.It is described in more excellent scheme Shell phase layer metal includes simultaneously Pt and Pd mixture, and wherein the weight ratio of Pt and Pd is (0.1~8): 1, Pt and Pd is thick in raising The selective hydrogenation activity aspect of cycle compound has synergistic effect.
The fused ring compound selective hydrocatalyst, based on parts by weight, nuclear phase layer tenor are catalyst 0.01-15 part of gross weight, prioritization scheme are 0.05-8 parts；Shell phase layer tenor is 0.01-5 part of overall catalyst weight, optimization 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 fused ring compound is selective to be added The preparation method of hydrogen catalyst, comprising:
A) salt of containing nuclear phase layer metal is dissolved in water or non-aqueous solution, then by precipitating, absorption, the method impregnated in carrier One layer of metallic compound of upper load roasts in 400-600 DEG C after dry, the catalyst I with nuclear phase layer structure is made.
B) salt containing shell phase layer metal is dissolved in water or non-aqueous solution, then negative by dipping, precipitating or coating process It is loaded on the catalyst I with nuclear phase layer structure, is roasted after dry in 400-600 DEG C, fused ring compound selective hydrogenation is made Catalyst.
Wherein, a) metal in step selected from zinc compound, copper-containing compound, containing in cadmium compound or Ag-containing compound At least one, wherein above-mentioned metal be selected from zinc nitrate, zinc chloride, zinc acetate, copper nitrate, copper carbonate, copper chloride, cadmium nitrate Or at least one of silver nitrate；The non-aqueous solution is selected from one of alcohol compound, ketone compounds, petroleum ether, on State one of non-aqueous solution selection ethyl alcohol, acetone, hexamethylene, normal heptane or toluene；B) metal salt in step is selected from platiniferous Compound, containing palladium compound, at least one of containing iridic compound, metal salt be selected from chloroplatinic acid, dinitro platinum ammonium, palladium chloride, At least one of palladium nitrate, iridium chloride, chloro-iridic acid；The non-aqueous solution is selected from alcohol compound, ketone compounds, petroleum ether One of, one of above-mentioned non-aqueous solution selection ethyl alcohol, acetone, hexamethylene, normal heptane or toluene.The catalyst is anti- Answering temperature is 100-500 DEG C, reaction pressure 1.0-5MPa, and hydrogen hydrocarbon molar ratio is 1-8, under the conditions of feed weight air speed is 1-20 It is reacted.
In the present invention, based on the interaction between nuclear shell carried metal, the electronic characteristic of shell metallic can be effectively adjusted, To which modulation shell metallic is to aromatics absorption intensity, the selective hydrogenation activity to condensed-nuclei aromatics is improved.The catalyst treatment contains When condensed-nuclei aromatics material, there is the advantages of condensed-nuclei aromatics selective hydrogenation rate 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, the certain zinc nitrate solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings 4 Hour, the modified catalyst A1 that Zn content is 5% (wt) is made and obtains the certain platinum acid chloride solution of catalyst A1 incipient impregnation Platinum content is the nucleocapsid metal layer catalyst B1 of 0.3% (wt).
5 grams of nucleocapsid metal layer catalyst B1 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to It 350 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total Weight space velocity 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 toluene: Naphthalene=90:10 (weight), reactivity worth is as shown in table 1.Wherein, R2/R1 indicates naphthalene weight hydrogenation rate and toluene by weight hydrogenation rate The ratio between, catalyst has been reacted to the hydrogenation selectivity of condensed-nuclei aromatics.
[embodiment 2]
Take 20 grams of alumina balls carriers, the certain copper nitrate solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings 4 Hour, the modified catalyst A2 that copper content is 5% (wt) is made and obtains the certain platinum acid chloride solution of catalyst A2 incipient impregnation Platinum content is the nucleocapsid metal layer catalyst B2 of 0.3% (wt).
5 grams of nucleocapsid metal layer catalyst B2 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to It 350 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total Weight space velocity 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 toluene: Naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[embodiment 3]
Take 20 grams of alumina balls carriers, the certain zinc nitrate solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings 4 Hour, the modified catalyst A3 that Zn content is 2% (wt) is made and obtains the certain platinum acid chloride solution of catalyst A3 incipient impregnation Platinum content is the nucleocapsid metal layer catalyst B3 of 0.3% (wt).
5 grams of nucleocapsid metal layer catalyst B3 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to It 350 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total Weight space velocity 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 toluene: Naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[embodiment 4]
Take 20 grams of alumina balls carriers, the certain zinc nitrate solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings 4 Hour, the modified catalyst A4 that Zn content is 5% (wt) is made and obtains the certain chlorine palladium acid solution of catalyst A4 incipient impregnation Palladium content is the nucleocapsid metal layer catalyst B4 of 0.3% (wt).
5 grams of nucleocapsid metal layer catalyst B4 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to It 350 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total Weight space velocity 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 toluene: Naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[embodiment 5]
Take 20 grams of alumina balls carriers, the certain zinc nitrate solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings 4 Hour, the modified catalyst A5 that Zn content is 5% (wt) is made, by the certain aqueous solution of chloraurate of catalyst A5 incipient impregnation, Obtain the nucleocapsid metal layer catalyst B5 that iridium content is 0.3% (wt).
5 grams of nucleocapsid metal layer catalyst B5 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to It 350 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total Weight space velocity 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 toluene: Naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[embodiment 6]
Take 20 grams of alumina balls carriers, the certain silver nitrate solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings 4 Hour, the modified catalyst A6 that silver content is 5% (wt) is made, the certain chloroplatinic acid ethyl alcohol of the isometric co-impregnation of catalyst A6 is molten Liquid obtains the nucleocapsid metal layer catalyst B6 that platinum content is 0.3% (wt).
5 grams of nucleocapsid metal layer catalyst B6 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to It 350 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total Weight space velocity 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 toluene: Naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[embodiment 7]
Take 20 grams of alumina balls carriers, the certain nitric acid cadmium solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings 4 Hour, the modified catalyst A7 that cadmium content is 5% (wt) is made and obtains the certain platinum acid chloride solution of catalyst A7 incipient impregnation Platinum content is the nucleocapsid metal layer catalyst B7 of 0.3% (wt).
5 grams of nucleocapsid metal layer catalyst B7 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to It 350 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total Weight space velocity 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 toluene: Naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[embodiment 8]
Take 20 grams of alumina balls carriers, the certain zinc nitrate of incipient impregnation and copper nitrate solution, 120 DEG C drying 4 hours, 550 DEG C roast 4 hours, and it is 2% (wt) that Zn content, which is made, and copper content is the modified catalyst A8 of 3% (wt), by catalyst A8 etc. The certain platinum acid chloride solution of volume impregnation obtains the nucleocapsid metal layer catalyst B8 that platinum content is 0.3% (wt).
5 grams of nucleocapsid metal layer catalyst B8 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to It 350 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total Weight space velocity 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 toluene: Naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[embodiment 9]
Take 20 grams of alumina balls carriers, the certain zinc nitrate of incipient impregnation and copper nitrate solution, 120 DEG C drying 4 hours, 550 DEG C roast 4 hours, and it is 2% (wt) that Zn content, which is made, and copper content is the modified catalyst A9 of 3% (wt), by catalyst A9 etc. The core that platinum content is 0.1% (wt), palladium content is 0.2% (wt) is made in the certain chloroplatinic acid of volume co-impregnation and palladium chloride solution Shell metal layer catalyst B9.
5 grams of nucleocapsid metal layer catalyst B9 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to It 350 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total Weight space velocity 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 toluene: Naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[embodiment 10]
Take 20 grams of alumina balls carriers, the certain zinc nitrate of incipient impregnation and copper nitrate solution, 120 DEG C drying 4 hours, 550 DEG C roast 4 hours, and it is 2% (wt) that Zn content, which is made, and copper content is the modified catalyst A10 of 3% (wt), by catalyst A10 Isometric certain chloroplatinic acid of co-impregnation and Chloroiridic Acid solution, obtained platinum content is 0.1% (wt), iridium content is 0.2% (wt's) Nucleocapsid metal layer catalyst B10.
5 grams of nucleocapsid metal layer catalyst B10 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and 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 first Benzene: naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[embodiment 11]
Take 20 grams of alumina balls carriers, the certain zinc nitrate of incipient impregnation and copper nitrate solution, 120 DEG C drying 4 hours, 550 DEG C roast 4 hours, and it is 2% (wt) that Zn content, which is made, and copper content is the modified catalyst A11 of 3% (wt), by catalyst A11 Isometric certain chloroplatinic acid of co-impregnation and palladium chloride solution, obtained platinum content is 0.05% (wt), palladium content is 0.25% (wt) Nucleocapsid metal layer catalyst B11.
5 grams of nucleocapsid metal layer catalyst B11 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and 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 first Benzene: naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[embodiment 12]
Take 20 grams of alumina balls carriers, the certain zinc nitrate of incipient impregnation and copper nitrate solution, 120 DEG C drying 4 hours, 550 DEG C roast 4 hours, and it is 2% (wt) that Zn content, which is made, and copper content is the modified catalyst A12 of 3% (wt), by catalyst A12 Isometric certain chloroplatinic acid of co-impregnation and palladium chloride solution, obtained platinum content is 0.2% (wt), palladium content is 0.1% (wt's) Nucleocapsid metal layer catalyst B12.
5 grams of nucleocapsid metal layer catalyst B12 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and 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 first Benzene: naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[embodiment 13]
Take 20 grams of alumina balls carriers, the certain zinc nitrate of incipient impregnation and silver nitrate solution, 120 DEG C drying 4 hours, 550 DEG C roast 4 hours, and it is 2% (wt) that Zn content, which is made, and silver content is the modified catalyst A13 of 3% (wt), by catalyst A13 Isometric certain chloroplatinic acid of co-impregnation and palladium chloride solution, obtained platinum content is 0.05% (wt), palladium content is 0.25% (wt) Nucleocapsid metal layer catalyst B13.
5 grams of nucleocapsid metal layer catalyst B13 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and 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 first Benzene: naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[embodiment 14]
Take 20 grams of alumina balls carriers, the certain zinc nitrate of incipient impregnation and nitric acid cadmium solution, 120 DEG C drying 4 hours, 550 DEG C roast 4 hours, and it is 2% (wt) that Zn content, which is made, and cadmium content is the modified catalyst A14 of 3% (wt), by catalyst A14 Isometric certain chloroplatinic acid of co-impregnation and palladium chloride solution, obtained platinum content is 0.05% (wt), palladium content is 0.25% (wt) Nucleocapsid metal layer catalyst B14.
5 grams of nucleocapsid metal layer catalyst B14 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and 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 first Benzene: naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[embodiment 15]
Take 20 grams of alumina balls carriers, the certain copper nitrate of incipient impregnation and nitric acid cadmium solution, 120 DEG C drying 4 hours, 550 DEG C roast 4 hours, and it is 2% (wt) that copper content, which is made, and cadmium content is the modified catalyst A15 of 3% (wt), by catalyst A15 Isometric certain chloroplatinic acid of co-impregnation and palladium chloride solution, obtained platinum content is 0.05% (wt), palladium content is 0.25% (wt) Nucleocapsid metal layer catalyst B15.
5 grams of nucleocapsid metal layer catalyst B15 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and 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 first Benzene: naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[embodiment 16]
Take 20 grams of alumina balls carriers, the certain copper nitrate of incipient impregnation and silver nitrate solution, 120 DEG C drying 4 hours, 550 DEG C roast 4 hours, and it is 2% (wt) that copper content, which is made, and silver content is the modified catalyst A16 of 3% (wt), by catalyst A16 Isometric certain chloroplatinic acid of co-impregnation and palladium chloride solution, obtained platinum content is 0.05% (wt), palladium content is 0.25% (wt) Nucleocapsid metal layer catalyst B16.
5 grams of nucleocapsid metal layer catalyst B16 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and 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 first Benzene: naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[embodiment 17]
20 grams of balloon borne bodies of amorphous silica-alumina, the certain zinc nitrate of incipient impregnation and copper nitrate solution are taken, 120 DEG C of dryings 4 are small When, 550 DEG C roast 4 hours, and it is 2% (wt) that Zn content, which is made, and copper content is the modified catalyst A17 of 3% (wt), by catalyst The certain chloroplatinic acid of the isometric co-impregnation of A17 and palladium chloride solution, it is 0.05% (wt), palladium content 0.25% that platinum content, which is made, (wt) nucleocapsid metal layer catalyst B17.
5 grams of nucleocapsid metal layer catalyst B17 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and 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 first Benzene: naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[embodiment 18]
Take carrier made of 20 grams of dealuminium mordenites (Si/Al=100) and aluminium oxide, the certain zinc nitrate of incipient impregnation And copper nitrate solution, 120 DEG C drying 4 hours, 550 DEG C roast 4 hours, be made Zn content be 2% (wt), copper content 3% (wt) platinum content is made in the certain chloroplatinic acid of the isometric co-impregnation of catalyst A18 and palladium chloride solution by modified catalyst A18 For 0.05% (wt), the nucleocapsid metal layer catalyst B18 that palladium content is 0.25% (wt).
5 grams of nucleocapsid metal layer catalyst B18 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and 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 first Benzene: naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[comparative example 1]
20 grams of alumina balls carriers are taken, the certain platinum acid chloride solution of incipient impregnation obtains the catalysis that platinum content is 0.3% (wt) Agent 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 toluene: naphthalene=90:10 (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 0.05% (wt), palladium content is the catalyst B20 of 0.25% (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 toluene: naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
[comparative example 3]
20 grams of alumina balls carriers, the certain zinc nitrate of incipient impregnation and copper nitrate solution solution are taken, 120 DEG C of dryings 4 are small When, 550 DEG C roast 4 hours, and it is 2% (wt) that Zn content, which is made, and copper content is the modified catalyst B21 of 3% (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 toluene: naphthalene=90:10 (weight), reactivity worth is as shown in table 1.
Table 1

Claims (8)

1. a kind of fused ring compound selective hydrocatalyst, comprising:
A) contain nonacid or faintly acid porous carrier, and load thereon
B) at least two metallic elements or compound selected from VIII, I B, II B of nuclear shell distribution.
2. fused ring compound selective hydrocatalyst according to claim 1, it is characterised in that nonacid or faintly acid Porous carrier is selected from least one of aluminium oxide, silica, magnesia, amorphous silica-alumina, kaolin, alumino-silicate.
3. fused ring compound selective hydrocatalyst according to claim 1, it is characterised in that the nuclear phase layer metal At least one of metal and its compound selected from Zn, Cu, Cd, Ag.
4. fused ring compound selective hydrocatalyst according to claim 1, it is characterised in that the shell phase layer metal Selected from least one of Pt, Pd, Ir metal and its compound.
5. fused ring compound selective hydrocatalyst according to claim 1, which is characterized in that based on parts by weight, Nuclear phase layer tenor is 0.01-15 part of overall catalyst weight.
6. fused ring compound selective hydrocatalyst according to claim 1, which is characterized in that based on parts by weight, Shell phase layer tenor is 0.01-5 part of overall catalyst weight.
7. a kind of preparation method of any one fused ring compound selective hydrocatalyst described in -6 according to claim 1, It is characterised by comprising:
A) salt of containing nuclear phase layer metal is dissolved in water or non-aqueous solution, then by precipitating, physics bonding, the method impregnated in carrier One layer of metallic compound of upper load roasts in 400-600 DEG C after dry, the catalyst I with nuclear phase layer structure is made；
B) salt containing shell phase layer metal is dissolved in water or non-aqueous solution, then is carried on by dipping, precipitating or coating process It on catalyst I with nuclear phase layer structure, is roasted after dry in 400-600 DEG C, fused ring compound selective hydrogenation catalysis is made Agent；
Wherein, a) metal in step selected from zinc compound, copper-containing compound, containing in cadmium compound or Ag-containing compound extremely Few one kind, the non-aqueous solution are selected from one of alcohol compound, ketone compounds, petroleum ether；；B) metal salt in step Selected from compound containing platinum, containing palladium compound, at least one of containing iridic compound, the non-aqueous solution be selected from alcohol compound, One of ketone compounds, petroleum ether.
8. a kind of method of fused ring compound selective hydrogenation, using any one catalysis described in claim 1~7 Agent, 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 1-20.
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JP2018153138A JP7158953B2 (en) 2017-08-18 2018-08-16 Catalyst for producing light aromatic hydrocarbons from heavy aromatic hydrocarbons, production method and application thereof
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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
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