CN101966467B - Catalyst for C8 aromatics isomerization reaction technology and preparation method thereof - Google Patents
Catalyst for C8 aromatics isomerization reaction technology and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for C8 aromatics isomerization reaction technology and a preparation method thereof. The composite reaction catalyst compounded by two different molecular sieve components modified by different methods according to a certain ratio, wherein one component has high-selectivity catalytic action on xylene isomerization and the other component has shape selective catalysis action on ethylbenzene deethylation. Due to the high-selectivity catalytic action of the composite molecular sieve catalyst, high-selectivity catalysis for dealkylation reaction of ethylbenzene in C8 mixed aromatics and the reaction that m-xylene and o-xylene are isomerized into p-xylene can be simultaneously realized. In the reaction technology of isomerization and dealkylation in the C8 mixed aromatics, a fixed bed reactor is adopted, the C8 mixed aromatics are taken as raw materials (an aromatic mixture mainly comprises m-xylene, o-xylene and ethylbenzene) and subjected to reaction at the temperature of between 350 and 460 DEG C and the airspeed of 2.5 to 15h<-1> and under the pressure of 0.5 to 3.0MPa. The reaction catalyst has high reaction activity, selectivity and stability, simplifies the process flow of the reaction and can obviously reduce the energy consumption and production cost.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method that is used for the isomerization of C-8 aromatics reaction process.
Background technology
Paraxylene (p-X) is one of main basic organic of petrochemical industry, in numerous chemical production field such as chemical fibre, synthetic resin, agricultural chemicals, medicine, plastics purposes is widely arranged.At present, through with C8 aronmatic C
8Meta-xylene m-X, ortho-xylene o-X isomery turn to paraxylene among the A, and are that the major technique of producing paraxylene is gone up in industry with the method that ethylbenzene (EB) transforms xylenes or benzene.In recent years, along with the swift and violent increase of terephthalic acid (TPA) (PTA) production capacity, demonstrate the paraxylene situation that supply falls short of demand in China, the isomerization catalysis technique that this shows xylenes is an important topic in the chemical production field.
At present, the isomerization of C-8 aromatics catalyst technology can be divided into two types according to the effect difference that ethylbenzene (EB) is transformed: one type is the EB dealkylation catalyst, and promptly m-X, o-X carry out isomerization reaction in the reaction, and ethylbenzene EB takes off alkyl generation benzene and transformed; The another kind of EB of being isomerization bifunctional catalyst (noble metal that all contains higher amount), xylenes and EB participate in isomerization reaction; The advantage of latter's double-function catalyzing isomerate process is that reaction process is simple, and ethylbenzene can be converted into xylenes, but that major defect is the low loss ratio with the open loop of xylenes hydrogenation of conversion ratio of ethylbenzene is higher.Desirable C
8The A arene isomerization catalyst can have high xylene isomerization rate and low aromatic hydrocarbons cracking loss under high EB activity of conversion.
From present circumstances and technology trends from now on, because energy prices go up and energy-saving and cost-reducing increase in demand, and EB takes off the restriction that alkyl does not receive chemical balance, can under high conversion, convert it into benzene, and make C
8The concentration of PX increases in the aromatic hydrocarbons, helps the separation of PX.Therefore, adopt EB to take off alkyl type isomerization catalyst at present and be obvious ascendant trend, become mainstream development direction now, it is very fast that EB is taken off the increase in demand of alkyl type isomerization catalyst.
EB is taken off alkyl to be transformed the key technical problem that type catalyst need solve and be: catalyst should be able to adapt to EB content high in the raw material, product is at utmost formed keeping near the thermodynamical equilibrium of xylenes.Simultaneously catalyst should suppress side reactions such as incident xylenes disproportionation, xylenes transalkylation, xylenes demethylation and hydrocracking, under the least possible condition of xylene loss, has stability preferably.
The ZSM-5 molecular sieve that MHAI (high activity isomery) method of Mobil company exploitation in recent years adopts two kinds of Different Silicon aluminum ratios to form is processed two kinds of different catalysts with binding agent respectively again, fills in two positions up and down of reactor.Its catalyst of separating reactor top mainly is to make ethylbenzene dealkylation and Fei Fang cracking, and the lower catalytic agent act as xylene isomerization.Though MHAI method activity is high, selectivity is better; But before using, must handle by these two kinds of catalyst through the presulfurization of reactor original position; And catalyst can not use on radial reactor and shell and tube reactor; Regeneration behind the catalyst coking inactivation is also than difficult and complicated, so limited its commercial Application simultaneously.
CN200680022943.8 relate to a kind of in two order districts with the isomerized method of the non-equilibrium mixture of alkylaromatic hydrocarbon, wherein first district uses not catalyst made from platonic and under the condition that does not have hydrogen, operates, the use of second district comprises the catalyst of molecular sieve and platinum group metal component; Thereby from mixture, obtain comparing the paraxylene of productive rate raising with existing method; But catalyst regeneration is difficult, and technological operation is complicated, and is high to equipment requirements; Once investment is big, and energy consumption is high.
EP 0923512 releases three xylene isomerization catalyst systems and is applicable to xylene isomerization and EB conversion reaction process; This system is made up of the catalyst of three kinds of series connection: first catalyst is used for Transformed E B; Second catalyst is used for hydrogenation (adopting with the aluminium oxide is the molybdenum catalyst of carrier), and the 3rd catalyst is used for xylene isomerization.This invention has solved the quick coking problem of catalyst, and coking especially takes place when EB accomplishes the transalkylation reaction conversion easily, has developed three bed process paths of less expensive simultaneously.Traditional double bed xylene isomerization catalyst is made up of EB reforming catalyst component and xylene isomerization catalyst component; Owing to produce ethene on the EB reforming catalyst; Cause the xylene isomerization catalyst deactivation rate too high; This invention is provided with hydrogenation catalyst and has solved the inactivation problem between EB reforming catalyst component and xylene isomerization catalyst component, hydrogenation catalyst can be converted into ethane in a large number with ethene, and other components in the product are not had any harmful effect; But this exists the antigravity system flow process complicated difficult with regeneration, and the technological operation trouble is high to equipment requirements, and the high deficiency of energy consumption.
Hence one can see that, and present existing double bed xylene isomerization catalyst technology all exists reaction process and catalyst complicacy, difficult, high to consersion unit and operation requirement, the high higher distinct disadvantage of plant energy consumption of catalyst regeneration.So the exploitation of the efficient integer catalyzer of carbon eight BTX aromatics high selectivity isomerization and dealkylation has very important actual demand.
Summary of the invention
In order to solve above-mentioned the problems of the prior art, the object of the present invention is to provide a kind of Catalysts and its preparation method that is used for the isomerization of C-8 aromatics reaction process.This catalysts is made up of by certain ratio is compound two kinds of different molecular sieve compositions through the distinct methods modification; Wherein a kind of composition has the high selectivity catalytic action of xylene isomerization; Another kind of composition has the shape selective catalysis effect that ethylbenzene takes off ethyl; Thereby make in two kinds of dissimilar molecular sieves that are reflected at different catalytic properties and obtained optimization respectively, and be presented as a kind of typical catalyst again with using in the operation on the mode of appearance.Through the efficient catalytic effect of composite molecular sieve catalyst of the present invention, can realize simultaneously that dealkylation and the meta-xylene of ethylbenzene in carbon eight BTX aromatics, the isomery of ortho-xylene turn to the high selectivity catalysis of paraxylene reaction; Catalysts also has the catalytic action of ethylene hydrogenation reaction simultaneously, to suppress the catalyst coking, to increase the service life.Carbon eight BTX aromatics isomerization with take off in the reaction process of alkyl, reaction molecular sieve catalyst of the present invention can be suitable for all types of axially, radially, use on the fixed bed reactors such as shell and tube.
A kind of catalyst that is used for the isomerization of C-8 aromatics reaction process that the present invention proposes, this catalyst is made up of two kinds of molecular sieve composition and binding agents through the distinct methods modification; Comprise following component in parts by weight:
(1) one of molecular sieve composition is SiO
2/ Al
2O
3Mol ratio is 10～80 parts of the Hydrogen Si-Al molecular sieves of 20～200 ten-ring pore structure, and this molecular sieve is modified the back use through liquid-phase silicone deposition processes and metallic compound load;
(2) two of the molecular sieve composition is SiO
2/ Al
2O
3Mol ratio is 10～80 parts of the Hydrogen Si-Al molecular sieves of 3～150 ten-ring or ten binary pore structures, and this molecular sieve uses behind modified metal oxide;
(3) all the other are adhesive oxides, and its gross weight umber satisfies 100 parts.
Among the present invention; One of said molecular sieve composition adopts in ZSM-5, NU-87, ZSM-11 or the EU-1 molecular sieve any; And to adopt dimethicone or polymethylphenyl siloxane fluid be that the liquid-phase silicone sedimentation that dressing agent carries out molecular sieve is modified, and its silica deposit amount is 2～10wt% of molecular sieve; Again above-mentioned siliceous deposits molecular sieve is further carried out the metallic compound load and modify, metallic compound adopts in molybdenum, nickel, platinum, palladium, rhodium, chromium, ruthenium or the cobalt arbitrary to multiple, and its content is counted 0.05～9wt% of molecular sieve with metal.
Among the present invention; Two of said molecular sieve composition adopts in Beta, ZSM-5, NU-87, ZSM-35, MCM-22, MOR, EU-1 or the Y molecular sieve any; And the load that at least a metal oxide in being selected from zinc, copper, iron, lanthanum, cerium, barium, magnesium or calcium carries out molecular sieve modifies, and its content is counted 0.1～12wt% of molecular sieve with metal.
Among the present invention, said adhesive oxides adopts aluminium oxide or silica.
The reaction process of catalysts of the present invention is: adopt fixed bed reactors; The C8 aronmatic raw material is to be a kind of aromatic hydrocarbons mixture of master with meta-xylene, ortho-xylene and ethylbenzene; At 350～460 ℃ of reaction temperatures, reaction pressure 0.5～3.0MPa, reaction velocity is under 2.0～15h-1; And using hydrogen as the reaction carrier gas, carrier gas/reactant ratio is 1～6: 1 (mol/mol).
The Preparation of catalysts method that is used for the isomerization of C-8 aromatics reaction process that the present invention proposes, concrete steps are following:
(1) one of molecular sieve composition in the catalysts: the petroleum ether solution of a kind of employing 8～25wt% dimethicone or polymethylphenyl siloxane fluid in ZSM-5, NU-87, ZSM-11 or the EU-1 zeolite is flooded; Benzinum is removed in the volatilization of dipping back; Again 500～530 ℃ of following roastings, promptly accomplish the liquid-phase silicone sedimentation of molecular sieve and modify after 120 ℃ of dryings; Behind at least a metallic compound in above-mentioned siliceous deposits molecular sieve molybdenum, nickel, platinum, palladium, rhodium, chromium, ruthenium or the cobalt or nitrate solution dipping; Molecular sieve is following dry 2 hours at 120 ℃; Then 450～560 ℃ of following roastings 2 hours; Promptly accomplish the further metal oxide supported modification of molecular sieve, obtain one of molecular sieve composition;
(2) two of the molecular sieve composition in the catalysts: will be selected from SiO
2/ Al
2O
3Mol ratio be among 20～200 Beta, ZSM-5, NU-87, ZSM-35, MCM-22, MOR, EU-1 or the Y any molecular sieve with at least a metal-nitrate solutions dipping that is selected from zinc, copper, iron, lanthanum, cerium, barium, magnesium, the calcium after; Molecular sieve is following dry 2 hours at 120 ℃; Then 480～550 ℃ of following roastings 2 hours; Promptly accomplish the metal oxide supported modification of molecular sieve, obtain two of molecular sieve composition;
(3) with above-mentioned two kinds mixing with the 1/10-1/1 weight ratio through modifying different molecular sieve composition; Method through bonding oxide agent and molecular sieve mixing granulation or extrusion modling is carried out moulding; Following dry 2 hours after the moulding at 120 ℃; 480～550 ℃ of following roastings 2 hours, promptly get required product then.
The present invention adopts fixed bed reactors, uses hydrogen as the reaction carrier gas, carries out the isomerized reaction of taking off ethyl reaction and meta-xylene, ortho-xylene of ethylbenzene in the C8 aronmatic.Reactor used internal diameter 20mm, length 600mm, stainless steel; The bead that it is 5mm that reactor bottom is filled one section diameter is as support, and the about 11cm of catalyst that fill at the middle part, the bead that fill on top play the effect of preheating and vaporization raw material; Mixed xylenes in the raw material (containing meta-xylene and ortho-xylene) and ethylbenzene mix with hydrogen, react through beds from top to bottom.
Raw material uses C
8BTX aromatics in mass fraction at meta-xylene 35-65wt%, ortho-xylene 15-30wt%, in the proportion of ethylbenzene 5-30wt%, experimental data adopts following formula calculating:
The present invention adopts fixed bed reactors, and through the efficient catalytic effect of catalyst of the present invention, simultaneously the highly selective isomery that carries out dealkylation and meta-xylene, the ortho-xylene of ethylbenzene in carbon eight BTX aromatics turns to paraxylene and reacts.This catalysts has that reaction process is simple, reactivity and selectivity height and the good characteristics of reaction stability.
Technical method of the present invention uses the catalyst of the composite molecular screen of a kind of compositing formula and preparation method's uniqueness as active component in single reactor; This catalyst is fit to the replacement catalyst and the transformation of existing process units easily; Both can improve carbon eight BTX aromatics isomerization and dealkylation activity and selectivity, and can promote the yield of product again.Above-mentioned technical characterictic makes in this invention catalyst and the present commercial production employed catalyst compare, and have following remarkable advantages: not only make production technology and simplified equipment, more convenient operation reduces production costs; And under higher reaction velocity, paraxylene isomerization rate and conversion of ethylbenzene are higher, and xylene loss is also less, and reaction stability is good, and the catalyst runs cycle is long.
The specific embodiment
Further specify the present invention through embodiment below.
Embodiment 1:
1) gets SiO
2/ Al
2O
3Mol ratio is 50 parts in 60 a Hydrogen ZSM-11 molecular sieve; Adopt the petroleum ether solution of 8% polymethylphenyl siloxane fluid to carry out the molecular sieve dipping, behind the dipping volatilization of solvent benzinum is removed, 120 ℃ of dry backs are 530 ℃ of following roastings; Promptly accomplish ZSM-11 liquid-phase silicone sedimentation and modify, obtain 3.1wt%SiO
2/ ZSM-11; Above-mentioned molecular sieve further again with 3.0wt% ammonium molybdate solution dipping, 480 ℃ of following roastings 2 hours, is promptly accomplished the burning molybdenum load of molecular sieve and modified after under 120 ℃ dry 2 hours, obtain 1.8wt%Mo/3.1wt%SiO
2/ ZSM-11; 2) get SiO
2/ Al
2O
3Mol ratio is 40 parts in 24 a Hydrogen Beta molecular sieve, with molecular sieve with 4.0wt% lanthanum nitrate hexahydrate dipping back 120 ℃ dry 2 hours down, then 500 ℃ of following roastings 2 hours, promptly accomplish the load of burning lanthanum and modify, obtain 2.3wt%La/Beta.3) with above-mentioned two kinds after modification different molecular sieve composition ZSM-11 and Beta mix; Adding the aluminium oxide bonding agent mixes with molecular sieve for 10 parts again; Add then and carry out extruded moulding after the rare nitric acid of a certain amount of 3wt% is fully mediated evenly, descended dry 2 hours at 120 ℃ then, again 550 ℃ of following roastings 2 hours; Promptly accomplish the preparation process of entire reaction molecular sieve catalyst, be designated as catalyst I.
Embodiment 2:
1) gets SiO
2/ Al
2O
3Mol ratio is 30 parts in 25 a Hydrogen ZSM-5 molecular sieve; Adopt the petroleum ether solution of 15% methyl-silicone oil to carry out the molecular sieve dipping, behind the dipping volatilization of solvent benzinum is removed, 120 ℃ of dry backs are 500 ℃ of following roastings; Promptly accomplish ZSM-5 liquid-phase silicone sedimentation and modify, obtain 5.7wt%SiO
2/ ZSM-5; Above-mentioned molecular sieve further again with 1.2wt% palladium nitrate solution dipping, 550 ℃ of following roastings 2 hours, is promptly accomplished the burning palladium load of molecular sieve and modified after under 120 ℃ dry 2 hours, obtain 0.58wt%Pd/6.7wt%SiO
2/ ZSM-5; 2) get SiO
2/ Al
2O
3Mol ratio is 50 parts in 20 a Hydrogen MCM-22 molecular sieve, with molecular sieve with 7.0wt% magnesium nitrate solution dipping back 120 ℃ dry 2 hours down, then 480 ℃ of following roastings 2 hours, promptly accomplish the magnesium-supported modification of burning, obtain 3.9wt%Mg/MCM-22.3) with above-mentioned two kinds after modification different molecular sieve composition ZSM-5 and MCM-22 mix; Adding the silica bonding agent mixes with molecular sieve for 20 parts again; Add then and carry out extruded moulding after the rare nitric acid of a certain amount of 3wt% is fully mediated evenly, descended dry 2 hours at 120 ℃ then, again 510 ℃ of following roastings 2 hours; Promptly accomplish the preparation process of entire reaction molecular sieve catalyst, be designated as catalyst I I.
Embodiment 3:
1) gets SiO
2/ Al
2O
3Mol ratio is 10 parts in 20 a Hydrogen EU-1 molecular sieve; Adopt the petroleum ether solution of 20% methyl-silicone oil to carry out the molecular sieve dipping, behind the dipping volatilization of solvent benzinum is removed, 120 ℃ of dry backs are 490 ℃ of following roastings; Promptly accomplish EU-1 liquid-phase silicone sedimentation and modify, obtain 8.2wt%SiO
2/ EU-1; Above-mentioned molecular sieve further again with 12.5wt% nickel nitrate solution dipping, 510 ℃ of following roastings 2 hours, is promptly accomplished the burning Ni of molecular sieve and modified after under 120 ℃ dry 2 hours, obtain 8.7wt%Ni/6.7wt%SiO
2/ EU-1; 2) get SiO
2/ Al
2O
3Mol ratio is 50 parts in 8 a Hydrogen MOR molecular sieve, with molecular sieve with 1.0wt% cerous nitrate solution dipping back 110 ℃ dry 2 hours down, then 490 ℃ of following roastings 2 hours, promptly accomplish the load of burning cerium and modify, obtain 0.19wt%Ce/MOR.3) with above-mentioned two kinds after modification different molecular sieve composition MOR and EU-1 mix; Adding the silica bonding agent mixes with molecular sieve for 40 parts again; Add then and carry out extruded moulding after the rare nitric acid of a certain amount of 3wt% is fully mediated evenly, descended dry 2 hours at 120 ℃ then, again 480 ℃ of following roastings 2 hours; Promptly accomplish the preparation process of entire reaction molecular sieve catalyst, be designated as catalyst I II.
Embodiment 4:
1) gets SiO
2/ Al
2O
3Mol ratio is 45 parts in 198 a Hydrogen NU-87 molecular sieve; Adopt the petroleum ether solution of 25% polymethylphenyl siloxane fluid to carry out the molecular sieve dipping, behind the dipping volatilization of solvent benzinum is removed, 120 ℃ of dry backs are 520 ℃ of following roastings; Promptly accomplish NU-87 liquid-phase silicone sedimentation and modify, obtain 12.0wt%SiO
2/ NU-87; Above-mentioned molecular sieve further again with 0.25wt% platinum acid chloride solution dipping, 550 ℃ of following roastings 2 hours, is promptly accomplished the compound loaded modification of metal platinum of molecular sieve after under 120 ℃ dry 2 hours, obtain 0.08wt%Pt/12.0wt%SiO
2/ NU-87; 2) get SiO
2/ Al
2O
3Mol ratio is 45 parts in 149 a Hydrogen ZSM-5 molecular sieve, with molecular sieve with 18.0wt% zinc nitrate solution dipping back 120 ℃ dry 2 hours down, then 520 ℃ of following roastings 2 hours, promptly accomplish the metal zinc oxide load and modify, obtain 11.9wt%Zn/ZSM-5.3) with above-mentioned two kinds after modification different molecular sieve composition NU-87 and ZSM-5 mix; Adding the silica bonding agent mixes with molecular sieve for 10 parts again; Add then and carry out extruded moulding after the rare nitric acid of a certain amount of 3wt% is fully mediated evenly, descended dry 2 hours at 120 ℃ then, again 480 ℃ of following roastings 2 hours; Promptly accomplish the preparation process of entire reaction molecular sieve catalyst, be designated as catalyst I V.
Embodiment 5:
Adopt fixed bed reactors, use hydrogen, carry out the isomerized reaction of taking off ethyl reaction and meta-xylene, ortho-xylene of ethylbenzene in the C8 aronmatic as the reaction carrier gas.Reactor used internal diameter 20mm, length 600mm, stainless steel; The bead that it is 5mm that reactor bottom is filled one section diameter is as support, and the about 11cm of catalyst height that fill at the middle part, the bead that fill on top play the effect of preheating and vaporization raw material; Include mixed xylenes in the raw material (containing meta-xylene 55.2wt% and ortho-xylene 23.7wt%) and ethylbenzene 21.1wt%; Raw material with after hydrogen mixes from top to bottom through beds, reaction condition is that 350～460 ℃ of reaction temperatures, reaction pressure 0.5～3.0MPa, reaction velocity are 2.0～15h
-1Down, and use hydrogen as the reaction carrier gas, carrier gas/reactant ratio is 1～6: 1 (mol/mol), and concrete catalyst system therefor and reaction condition are seen table 1.To design temperature, feed reaction raw materials with measuring pump through temperature programming in 100 minutes, sample calculates reaction conversion ratio and selectivity, xylene loss through gas chromatographic analysis.
Table 1. practical implementation reaction condition and catalytic reaction result
The reaction result data show in the table 1; Use composite molecular sieve catalyst of the present invention the isomerization reaction of xylenes and ethylbenzene to take off the catalytic activity that not only has two reactions in the ethyl reaction all higher; And the loss late of xylenes is also less in the reaction; Explain that catalyst can suppress side reaction such as xylenes disproportionation dramatically, make whole selectivity high, and can simplify production technology, the purpose of reached energy-saving and cost-reducing, practicing thrift cost; It is the high-performance paraxylene isomerization catalyst of new generation that meets the commercial Application demand.
Claims (3)
1. one kind is used for the isomerization of C-8 aromatics catalyst for reaction, it is characterized in that said catalyst is made up of two kinds of molecular sieve composition and binding agents through the distinct methods modification; Comprise following component in parts by weight:
(1) one of molecular sieve composition is SiO
2/ Al
2O
3Mol ratio is 10～80 parts of the Hydrogen Si-Al molecular sieves of 20～200 ten-ring pore structure, and this molecular sieve is modified the back use through liquid-phase silicone deposition processes and metallic compound load;
(2) two of the molecular sieve composition is SiO
2/ Al
2O
3Mol ratio is 10～80 parts of the Hydrogen Si-Al molecular sieves of 3～150 ten-ring or ten binary pore structures, and this molecular sieve uses behind modified metal oxide;
(3) all the other are adhesive oxides, and its gross weight umber satisfies 100 parts;
Wherein: one of said molecular sieve composition adopts in ZSM-5, NU-87, ZSM-11 or the EU-1 molecular sieve any; And to adopt dimethicone or polymethylphenyl siloxane fluid be that the liquid-phase silicone sedimentation that dressing agent carries out molecular sieve is modified, and its silica deposit amount is 2～10wt% of molecular sieve; Again above-mentioned siliceous deposits molecular sieve is further carried out the metallic compound load and modify, metallic compound adopts in molybdenum, nickel, platinum, palladium, rhodium, chromium, ruthenium or the cobalt arbitrary to multiple, and its content is counted 0.05～9wt% of molecular sieve with metal; Two of said molecular sieve composition adopts in Beta, ZSM-5, NU-87, ZSM-35, MCM-22, MOR, EU-1 or the Y molecular sieve any; And the load that at least a metal oxide in being selected from zinc, copper, iron, lanthanum, cerium, barium, magnesium or calcium carries out molecular sieve modifies, and its content is counted 0.1～12wt% of molecular sieve with metal.
2. the isomerization of C-8 aromatics catalyst for reaction that is used for according to claim 1 is characterized in that said adhesive oxides adopts aluminium oxide or silica.
3. preparation method who is used for the isomerization of C-8 aromatics catalyst for reaction as claimed in claim 1 is characterized in that concrete steps are following:
(1) one of molecular sieve composition in the catalysts: the petroleum ether solution of a kind of employing 8～25wt% dimethicone or polymethylphenyl siloxane fluid in ZSM-5, NU-87, ZSM-11 or the EU-1 molecular sieve is flooded; Benzinum is removed in the volatilization of dipping back; Again 500～530 ℃ of following roastings, promptly accomplish the liquid-phase silicone sedimentation of molecular sieve and modify after 120 ℃ of dryings; Behind at least a metal compound solution dipping in above-mentioned siliceous deposits molecular sieve molybdenum, nickel, platinum, palladium, rhodium, chromium, ruthenium or the cobalt; Molecular sieve is following dry 2 hours at 120 ℃; Then 450～560 ℃ of following roastings 2 hours; Promptly accomplish the further metal oxide supported modification of molecular sieve, obtain one of molecular sieve composition;
(2) two of the molecular sieve composition in the catalysts: will be selected from SiO
2/ Al
2O
3Mol ratio be among 3～150 Beta, ZSM-5, NU-87, ZSM-35, MCM-22, MOR, EU-1 or the Y any molecular sieve with at least a metal-nitrate solutions dipping that is selected from zinc, copper, iron, lanthanum, cerium, barium, magnesium, the calcium after; Molecular sieve is following dry 2 hours at 120 ℃; Then 480～550 ℃ of following roastings 2 hours; Promptly accomplish the metal oxide supported modification of molecular sieve, obtain two of molecular sieve composition;
(3) with above-mentioned two kinds mixing with 1/1 weight ratio through modifying different molecular sieve composition; Method through bonding oxide agent and molecular sieve mixing granulation or extrusion modling is carried out moulding; Descended dry 2 hours at 120 ℃ after the moulding,, promptly get required product then 480～550 ℃ of following roastings 2 hours.
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| CN113663718A (en) * | 2020-05-15 | 2021-11-19 | 中国石油天然气股份有限公司 | Ethylbenzene dealkylation type xylene isomerization reaction catalyst and preparation method thereof |
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