CN105498829A - Methanol aromatized catalyst as well as preparation method and application thereof - Google Patents
Methanol aromatized catalyst as well as preparation method and application thereof Download PDFInfo
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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Abstract
The invention provides a methanol aromatized catalyst. The catalyst comprises (1) an H-ZSM-5 molecular sieve mixture and (2) a metal modified element loaded on the H-ZSM-5 molecular sieve mixture, wherein the H-ZSM-5 molecular sieve mixture comprises an H-ZSM-5 first molecular sieve with a silicon-aluminum ratio of 18 to 75, and an H-ZSM-5 second molecular sieve with a silicon-aluminum ratio of 76 to 300, and the mass ratio of the H-ZSM-5 first molecular sieve to the H-ZSM-5 second molecular sieve is 1:(0.02 to 1); the metal modified element comprises a first metal modified element and a second metal modified element, wherein the first metal modified element is selected from Zn and Ga and the second metal modified element is selected from Ag, La, Cu, Ce, Mg, Cd, Fe and Mo; by the mass of metal elements, the mass sum of the first metal modified element and the second metal modified element is 0.1 percent to 8 percent of that of the H-ZSM-5 molecular sieve mixture and the ratio of amount of substance of the first metal modified element to the second metal modified element is 1:(0.1 to 1). The invention further relates to a preparation method of the methanol aromatized catalyst and application of the methanol aromatized catalyst to preparation of benzene, toluene and xylene.
Description
Technical field
The present invention relates to a kind of aromatization of methanol Catalysts and its preparation method for the preparation of aromatic hydrocarbons and application, and relate to particularly a kind of for Methanol for the aromatization of methanol Catalysts and its preparation method of benzene, toluene or dimethylbenzene and application.
Background technology
Benzene,toluene,xylene (BTX) in aromatic hydrocarbons is the important base stock of petrochemical industry, is widely used in the various fields such as the energy, traffic, material, agricultural chemicals, daily use chemicals.The aromatic hydrocarbons of China is mainly prepared by techniques such as oil catalytic reforming and pyrolysis gasoline hydrogenation extractings, depends critically upon petroleum resources.Along with the scarcity of China's oil resource and the further raising of external dependence degree, the limitation of traditional aromatics production technique highlights, in the urgent need to seeking a kind of that do not rely on fossil resources, new aromatics production technique.Thus, Methanol aromatic hydrocarbons (MethanoltoAromatics is called for short " MTA ") technology arouses widespread concern, and becomes one of focus of countries in the world researcher research.
Methanol aromatic hydrocarbons generally refers to methyl alcohol to be raw material, under the catalytic action of catalyst, carries out a series of reaction, prepares based on the aromatic hydrocarbons of benzene, toluene and dimethylbenzene (BTX).Methanol aromatic hydrocarbons technology is from Methanol hydrocarbon (MethanoltoHydrocarbons is called for short " MTH ") technical development.Researcher is devoted to the yield of the aromatics yield, particularly BTX improving Methanol aromatics process always, and the MTA catalyst wherein developing excellent performance is one of the key and difficult point that realize above-mentioned purpose.
ZSM-5 molecular sieve belongs to rhombic system, there is the mutual intersection duct of size uniform, a kind of straight tube shape duct (pore size is 0.54nm × 0.56nm) for ellipsoidal cross section, is another kind ofly approximately the Z-shaped duct (pore size is 0.52nm × 0.58nm) of circle for cross section.
Existing result of study shows, Hydrogen ZSM-5 molecular sieve (H-ZSM-5 molecular sieve) catalyst due to the pore structure of its uniqueness and acidic character, be MTA reaction the most effectively and one of catalyst of main research.But the MTA performance of traditional H-ZSM-5 molecular sieve is difficult to meet industrial requirement.At present, Mo
2c, Ga
2o
3, the metallic element such as Zn, Cu, Ag is normally used for modification H-ZSM-5 molecular sieve, to improving the aromatization of methanol performance of catalyst.The introducing of these metallic elements not only can change the acidity of molecular sieve catalyst, can also change specific area and the pore structure of molecular sieve catalyst, and then affects the MTA catalytic performance of H-ZSM-5 molecular sieve catalyst.Such as, the Zn/ZSM-5 catalyst that Wang Jinying etc. adopt excessive infusion process modification to prepare shows the Aromatization Activity being better than unmodified catalyst, wherein the Zn load capacity of 0.5% can improve aromatics yield 5% (chemistry of fuel journal, 2009,37 (5): 607-612).In addition, the Ag/ZSM-5 catalyst of the preparation such as Tian Tao shows excellent aromatization performance equally, and the aromatics yield under 475 DEG C and reaction velocity are the condition of 300mL/g/h is up to 64% (chemical industry is in progress, 2010,29:470-473).But the demand that the existing aromatics yield of MTA catalyst and the stability etc. of catalyst are still improved and space.
Summary of the invention
Therefore, an object of the present invention is to provide a kind of aromatization of methanol Catalysts and its preparation method, this catalyst has high aromatics yield, the advantages such as particularly high benzene, toluene and dimethylbenzene (being referred to as " BTX ") yield.Another object of the present invention is to provide aromatization of methanol catalyst and is preparing the application in benzene, toluene and dimethylbenzene.
The object of the invention is to be achieved through the following technical solutions.
On the one hand, the invention provides a kind of aromatization of methanol catalyst, described catalyst comprises:
(1) H-ZSM-5 molecular sieve mixture, described H-ZSM-5 molecular sieve mixture comprise silica alumina ratio be 18 ~ 75 H-ZSM-5 first molecular sieve and silica alumina ratio be 76 ~ 300 H-ZSM-5 second molecular sieve, and the mass ratio of described H-ZSM-5 first molecular sieve and described H-ZSM-5 second molecular sieve is 1:0.02 ~ 1; With
(2) the metal-modified element of described H-ZSM-5 molecular sieve mixture is carried on, described metal-modified element comprises the first metal-modified element and the second metal-modified element, wherein, described first metal-modified element is selected from Zn and Ga, described second metal-modified element is selected from Ag, La, Cu, Ce, Mg, Cd, Fe and Mo, and wherein, in metallic element quality, the quality sum of described first metal-modified element and described second metal-modified element is 0.1 ~ 8% of described H-ZSM-5 molecular sieve mixture quality, the amount of substance of described first metal-modified element and described second metal-modified element is than being 1:0.1 ~ 1.
In the present invention, described metal-modified element is generally be carried on described H-ZSM-5 molecular sieve mixture in the form of the oxide.
As used herein, term " silica alumina ratio " refers to the mol ratio of silica and aluminium oxide in molecular sieve, usually can be expressed as SiO
2/ Al
2o
3.
In the present invention, the ZSM-5 molecular sieve with Different Silicon aluminum ratio can be obtained by conventional preparation side, such as, the 13/502nd, describe in No. 607 U.S. Patent applications those.Then, by acid exchange, ZSM-5 molecular sieve is made H-ZSM-5 molecular sieve.
According to catalyst provided by the invention, wherein, the silica alumina ratio of described H-ZSM-5 first molecular sieve is preferably 25 ~ 65, is more preferably 25 ~ 45.
According to catalyst provided by the invention, wherein, the silica alumina ratio of described H-ZSM-5 second molecular sieve is preferably 80 ~ 100.
In some preferred embodiments, the silica alumina ratio of described H-ZSM-5 first molecular sieve is 25 ~ 45, and the silica alumina ratio of described H-ZSM-5 second molecular sieve is 80 ~ 100.
According to catalyst provided by the invention, wherein, in metallic element quality, the quality sum of described first metal-modified element and described second metal-modified element is 0.2 ~ 5% of described H-ZSM-5 molecular sieve mixture quality, is preferably 2 ~ 3%.
According to catalyst provided by the invention, wherein, the amount of substance of described first metal-modified element and described second metal-modified element is than being 1:0.2 ~ 0.6.
On the other hand, the invention provides a kind of method preparing described catalyst, said method comprising the steps of:
(1) by H-ZSM-5 first molecular sieve and the mixing of H-ZSM-5 second molecular sieve, thus obtained H-ZSM-5 molecular sieve mixture;
(2) in described H-ZSM-5 molecular sieve mixture, add metal-modified elemental precursors solution, be uniformly mixed, at 60 ~ 100 DEG C, leave standstill process; Wherein, described metal-modified elemental precursors solution comprises the first metal-modified elemental precursors and the second metal-modified elemental precursors, described first metal-modified elemental precursors is selected from nitrate or the sulfate of Zn and Ga, and described second metal-modified elemental precursors is selected from nitrate or the sulfate of Ag, La, Cu, Ce, Mg, Cd, Fe and Mo; With
(3) product that obtains in step (2) is dry, grinding and roasting, thus obtained aromatization of methanol catalyst.
According to method provided by the invention, wherein, described first metal-modified elemental precursors is nitrate or the sulfate of Zn, described second metal-modified elemental precursors is selected from nitrate or the sulfate of Ag, Cu and Cd, and also comprise ammonia in described metal-modified elemental precursors solution, the ratio of described first metal-modified element and the described amount of substance sum of the second metal-modified element and the amount of substance of ammonia is 1:6 ~ 1:16, is preferably 1:9 ~ 1:12.
According to method provided by the invention, wherein, the ammonia in described metal-modified elemental precursors solution adds with the form of ammoniacal liquor, and the mass percentage concentration of described ammoniacal liquor is 5 ~ 25%, is preferably 10 ~ 18%.
According to method provided by the invention, wherein, described metal-modified elemental precursors solution is prepared by the following method: (a) prepares the aqueous solution of described first metal-modified elemental precursors and described second metal-modified elemental precursors; (b) in the described aqueous solution, add ammoniacal liquor, and stir 0.5 ~ 2 hour at 25 ~ 40 DEG C.
According to preparation method provided by the invention, wherein, being uniformly mixed described in step (2) is carried out at 25 ~ 40 DEG C, and preferably, the time be uniformly mixed is 0.5 ~ 5 hour.
According to method provided by the invention, wherein, the temperature of the standing process described in step (2) is 60 ~ 100 DEG C, is preferably 70 ~ 90 DEG C.
According to preparation method provided by the invention, wherein, the time of the standing process described in step (2) is 4 ~ 48 hours, is preferably 2-24 hour, is more preferably 6 ~ 24 hours.
In some preferred embodiments, process 6 ~ 24 hours are left standstill at the standing process described in step (2) is included in 70 ~ 80 DEG C.
According to method provided by the invention, wherein, the drying described in step (3) and grinding operation can adopt conventional method known in the art.In some embodiments, dry temperature can be 80 ~ 120 DEG C.
According to method provided by the invention, wherein, the temperature of the roasting described in step (3) is 500 ~ 550 DEG C.
Another aspect, present invention also offers described aromatization of methanol catalyst and is preparing the application in benzene, toluene and dimethylbenzene.
Provided by the present invention prepare aromatization of methanol catalyst method and aromatization of methanol catalyst have but be not limited to following beneficial effect:
(1) do not wish that the present invention utilizes the difference of the acid intensity of the molecular sieve of Different Silicon aluminum ratio, the acid intensity of modulation aromatization of methanol, by the acting in conjunction of two kinds of molecular sieves, significantly enhances the Aromatization Activity of catalyst by theoretical restriction.
(2) do not wish by theoretical restriction, the form that the present invention forms complex compound by interpolation excessive ammonia and metal ion carries out modification to H-ZSM-5 molecular sieve, molecular sieve part desiliconization can be made under weakly alkaline condition simultaneously, form multi-stage porous, be conducive to realizing the acidity of molecular sieve and the modification of pore passage structure by simple step simultaneously, to raising BTX yield and stability, there is obvious effect.
Detailed description of the invention
Further illustrate the present invention below by specific embodiment, but should be understood to, these embodiments are only used for the use specifically described more in detail, and should not be construed as limiting the present invention in any form.
General description is carried out to the material used in the embodiment of the present invention and test method in this part.Although for realizing many materials that the object of the invention uses and method of operating is well known in the art, the present invention still describes in detail as far as possible at this.It will be apparent to those skilled in the art that within a context, if not specified, material therefor of the present invention and method of operating are well known in the art.
embodiment 1
The present embodiment is for illustration of aromatization of methanol Catalysts and its preparation method.Particularly, the preparation method of aromatization of methanol catalyst comprises the following steps:
(1) take silica alumina ratio be 25 H-ZSM-5 molecular sieve 25g and silica alumina ratio be 90 H-ZSM-5 molecular sieve 5g, be placed in reactor, mix.
(2) by the first metal-modified elemental precursors Zn (NO
3)
26H
2o and the second metal-modified elemental precursors AgNO
3be dissolved in 150ml deionized water, then drip the ammoniacal liquor 4.6ml of 15%, at room temperature stir 0.5h, obtain the mixed liquor of metal-modified elemental precursors and ammoniacal liquor; Wherein, the quality sum of Zn and Ag element accounts for the 2wt% of molecular sieve, and Zn (NO
3)
2and AgNO
3amount of substance than for 1:0.5.
(3) metal-modified elemental precursors step (2) obtained and the mixed liquor of ammoniacal liquor add in reactor, and at room temperature stir 3h, then raised temperature to 80 DEG C, leave standstill 24 hours.
(4) product step (3) obtained is taken out, and chilling is lowered the temperature, dry at 100 DEG C, obtains dried sample.
(5) dried sample step (4) obtained, through grinding, goes to Muffle furnace internal program and is warming up to 550 DEG C of roasting 4h, and obtained aromatization of methanol catalyst, is designated as MTA catalyst 1.
embodiment 2
The present embodiment is for illustration of aromatization of methanol Catalysts and its preparation method.Particularly, the preparation method of aromatization of methanol catalyst comprises the following steps:
(1) take silica alumina ratio be 37 H-ZSM-5 molecular sieve 26g and silica alumina ratio be 80 H-ZSM-5 molecular sieve 4g, be placed in reactor, mix.
(2) by the first metal-modified elemental precursors Zn (NO
3)
26H
2o and the second metal-modified elemental precursors La (NO
3)
36H
2o is dissolved in 150ml deionized water, at room temperature stirs 0.5h, obtains metal-modified elemental precursors mixed liquor; Wherein, the quality sum of Zn and La element accounts for the 3.0wt% of molecular sieve, and Zn (NO
3)
2with La (NO
3)
3amount of substance ratio be 1:0.3.
(3) the metal-modified elemental precursors solution that step (2) obtains is added in reactor, and at room temperature stir 2h, then raised temperature to 90 DEG C, leave standstill 24 hours.
(4) product step (3) obtained is taken out, and chilling is lowered the temperature, dry at 100 DEG C, obtains dried sample.
(5) dried sample step (4) obtained, through grinding, goes to Muffle furnace internal program and is warming up to 550 DEG C of roasting 4h, and obtained aromatization of methanol catalyst, is designated as MTA catalyst 2.
embodiment 3
The present embodiment is for illustration of aromatization of methanol Catalysts and its preparation method.Particularly, the preparation method of aromatization of methanol catalyst comprises the following steps:
(1) take silica alumina ratio be 37 H-ZSM-5 molecular sieve 20g and silica alumina ratio be 80 H-ZSM-5 molecular sieve 10g, be placed in reactor, mix.
(2) by the first metal-modified elemental precursors Ga
2(SO
4)
316H
2o and the second metal-modified elemental precursors Ce (NO
3)
36H
2o is dissolved in 150ml deionized water, at room temperature stirs 0.5h, obtains metal-modified elemental precursors mixed liquor; Wherein, the quality sum of Ga and Ce element accounts for the 2.5wt% of molecular sieve and Ga
2(SO
4)
3with Ce (NO
3)
3amount of substance ratio be 1:0.4 (namely the amount of substance ratio of Ga element and Ce element is 1:0.2).
(3) the metal-modified elemental precursors mixed liquor that step (2) obtains is added in reactor, and at room temperature stir 4h, then raised temperature to 90 DEG C, leave standstill 36 hours.
(4) product step (3) obtained is taken out, and chilling is lowered the temperature, dry at 100 DEG C, obtains dried sample.
(5) dried sample step (4) obtained, through grinding, goes to Muffle furnace internal program and is warming up to 550 DEG C of roasting 4h, and obtained aromatization of methanol catalyst, is designated as MTA catalyst 3.
embodiment 4
The present embodiment is for illustration of aromatization of methanol Catalysts and its preparation method.Particularly, the preparation method of aromatization of methanol catalyst comprises the following steps:
(1) take silica alumina ratio be 25 H-ZSM-5 molecular sieve 18g and silica alumina ratio be 97 H-ZSM-5 molecular sieve 12g, be placed in reactor, mix.
(2) by the first metal-modified elemental precursors Zn (NO
3)
26H
2o and the second metal-modified elemental precursors Cd (NO
3)
39H
2o is dissolved in 150ml deionized water, then drips the ammoniacal liquor 3.5ml of 15%, at room temperature stirs 0.5h, obtain the mixed liquor of metal-modified elemental precursors and ammoniacal liquor; Wherein, the quality sum of Zn and Cd element accounts for the 2.8wt% of molecular sieve, and Zn (NO
3)
2with Cd (NO
3)
3amount of substance ratio be 1:0.3.
(3) metal-modified elemental precursors step (2) obtained and the mixed liquor of ammoniacal liquor add in reactor, and at room temperature stir 3h, then raised temperature to 70 DEG C, leave standstill 36 hours.
(4) product step (3) obtained is taken out, and chilling is lowered the temperature, dry at 100 DEG C, obtains dried sample.
(5) dried sample step (4) obtained, through grinding, goes to Muffle furnace internal program and is warming up to 550 DEG C of roasting 4h, and obtained aromatization of methanol catalyst, is designated as MTA catalyst 4.
embodiment 5
The present embodiment is for illustration of aromatization of methanol Catalysts and its preparation method.Particularly, the preparation method of aromatization of methanol catalyst comprises the following steps:
(1) take silica alumina ratio be 45 H-ZSM-5 molecular sieve 27g and silica alumina ratio be 83 H-ZSM-5 molecular sieve 3g, be placed in reactor, mix.
(2) by the first metal-modified elemental precursors Zn (NO
3)
26H
2o and the second metal-modified elemental precursors Mg (NO
3)
26H
2o is dissolved in 150ml deionized water, then at room temperature stirs 0.5h, obtains modifier mixed liquor; Wherein, the quality sum of Zn and Mg element accounts for the 2.8wt% of molecular sieve, and Zn (NO
3)
2with Mg (NO
3)
2amount of substance ratio be 1:0.4.
(3) metal-modified elemental precursors step (2) obtained and the mixed liquor of ammoniacal liquor add in reactor, and at room temperature stir 5h, then raised temperature to 90 DEG C, leave standstill 12 hours.
(4) product step (3) obtained is taken out, and chilling is lowered the temperature, dry at 120 DEG C, obtains dried sample.
(5) dried sample step (4) obtained, through grinding, goes to Muffle furnace internal program and is warming up to 550 DEG C of roasting 4h, and obtained aromatization of methanol catalyst, is designated as MTA catalyst 5.
embodiment 6
The present embodiment is for illustration of aromatization of methanol Catalysts and its preparation method.Particularly, the preparation method of aromatization of methanol catalyst comprises the following steps:
(1) take the H-ZSM-5 molecular sieve 30g that silica alumina ratio is 25, be placed in reactor, mix.
(2) by the first metal-modified elemental precursors Zn (NO
3)
26H
2o and the second metal-modified elemental precursors AgNO
3be dissolved in 150ml deionized water, at room temperature stir 0.5h, obtain the mixed liquor of metal-modified elemental precursors; Wherein, the quality sum of Zn and Ag element accounts for the 2wt% of molecular sieve, and Zn (NO
3)
2and AgNO
3amount of substance ratio be 1:0.5.
(3) mixed liquor of metal-modified elemental precursors step (2) obtained adds in reactor, and at room temperature stirs 3h, then raised temperature to 80 DEG C, leaves standstill 24 hours.
(4) product step (3) obtained is taken out, and chilling is lowered the temperature, dry at 100 DEG C, obtains dried sample.
(5) dried sample step (4) obtained, through grinding, goes to Muffle furnace internal program and is warming up to 550 DEG C of roasting 4h, and obtained aromatization of methanol catalyst, is designated as MTA catalyst 6.
comparative example 1 ~ 4
Comparative example 1 ~ 4 adopt respectively silica alumina ratio be the H-ZSM-5 molecular sieve of 25,37,83 and 90 as a comparison.
comparative example 5
(1) take the H-ZSM-5 molecular sieve 30g that silica alumina ratio is 25, be placed in reactor, mix.
(2) by metal-modified elemental precursors Zn (NO
3)
26H
2o is dissolved in 150ml deionized water, at room temperature stirs 0.5h, obtains metal-modified elemental precursors solution; Wherein, the quality of Zn element accounts for the 2wt% of molecular sieve quality.
(3) the metal-modified elemental precursors solution that step (2) obtains is added in reactor, and at room temperature stir 3h, then raised temperature to 80 DEG C, leave standstill 24 hours.
(4) product step (3) obtained is taken out, and chilling is lowered the temperature, dry at 100 DEG C, obtains dried sample.
(5) dried sample step (4) obtained, through grinding, goes to Muffle furnace internal program and is warming up to 550 DEG C of roasting 4h, obtained aromatization of methanol catalyst.
comparative example 6
Adopt the method identical with comparative example 5 to carry out modification to the H-ZSM-5 molecular sieve that silica alumina ratio is 25, difference is: metal-modified elemental precursors is AgNO
3.
comparative example 7
(1) take the H-ZSM-5 molecular sieve 30g that silica alumina ratio is 90, be placed in reactor, mix.
(2) by metal-modified elemental precursors Zn (NO
3)
26H
2o is dissolved in 150ml deionized water, at room temperature stirs 0.5h, obtains metal-modified elemental precursors solution; Wherein, the quality of Zn element accounts for the 2wt% of molecular sieve quality.
(3) modifier solution that step (2) obtains is added in reactor, and at room temperature stir 3h, then raised temperature to 80 DEG C, leave standstill 24 hours.
(4) product step (3) obtained is taken out, and chilling is lowered the temperature, dry at 100 DEG C, obtains dried sample.
(5) dried sample step (4) obtained, through grinding, goes to Muffle furnace internal program and is warming up to 550 DEG C of roasting 4h, obtained aromatization of methanol catalyst.
comparative example 8
Adopt the method identical with comparative example 7 to carry out modification to the H-ZSM-5 molecular sieve that silica alumina ratio is 90, difference is: metal-modified elemental precursors is AgNO
3.
comparative example 9
(1) take the H-ZSM-5 molecular sieve 30g that silica alumina ratio is 25, be placed in reactor, mix.
(2) by the first metal-modified elemental precursors Zn (NO
3)
26H
2o and the second metal-modified elemental precursors AgNO
3be dissolved in 150ml deionized water, at room temperature stir 0.5h, obtain the mixed liquor of metal-modified elemental precursors; Wherein, the quality sum of Zn and Ag element accounts for the 2wt% of molecular sieve, and Zn (NO
3)
2and AgNO
3amount of substance ratio be 1:0.5.
(3) mixed liquor of metal-modified elemental precursors step (2) obtained adds in reactor, and at room temperature stirs 3h, then raised temperature to 80 DEG C, leaves standstill 24 hours.
(4) product step (3) obtained is taken out, and chilling is lowered the temperature, and filters and spends deionized water to neutral, dry at 100 DEG C, obtains dried sample.
(5) dried sample step (4) obtained, through grinding, goes to Muffle furnace internal program and is warming up to 550 DEG C of roasting 4h, obtained aromatization of methanol catalyst.
comparative example 10
Adopt the method identical with comparative example 9 to carry out modification to the H-ZSM-5 molecular sieve that silica alumina ratio is 90, difference is: molecular sieve used to be silica alumina ratio be 90 H-ZSM-5 molecular sieve.
embodiment 11
Embodiment 11 adopt silica alumina ratio be 25 H-ZSM-5 molecular sieve 25g and silica alumina ratio be the mixture of the H-ZSM-5 molecular sieve 5g of 90 as a comparison.
catalyst performance evaluation
Carry out performance evaluation to the catalyst of embodiment 1 ~ 6 and comparative example 1 ~ 11 respectively, its operational overview is as follows.The loaded catalyst of each evaluation is 3.0g, and with pure methyl alcohol for raw material, at 200 DEG C, pure methyl alcohol is first through being equipped with the preheater of inert stone sand, and then enter main reactor and carry out MTA reaction, liquid hourly space velocity (LHSV) is 2h
-1, reaction temperature is 420 DEG C, and system stagnation pressure is less than 0.05MPa, and the product of MTA can be divided into gas, water, oily three-phase, product through drainer cooling after, lighter hydrocarbons (C
1-C
5various alkene and alkane) etc. directly enter gas-chromatography on-line analysis with HP-PLOT-Q post as gas-phase product; Liquid phase is then collected by cold-trap, takes out after a certain period of time, is aqueous phase and oil phase with separatory funnel by liquid phase separation, and mainly aromatic hydrocarbons in oil phase, adopts the gas-chromatography off-line analysis with DB-WAX post; Then pass through the gas-chromatography off-line analysis with HP-PLOT-Q post containing unreacted methyl alcohol and a small amount of dimethyl ether (containing dimethyl ether as methanol conversion <100%) in aqueous phase, aqueous phase and oil phase adopt internal standard method analysis.Gas, water, oily all products are finally by normalization, and represent with the mass content of carbon back, reaction result lists in table 1.
The catalyst performance of table 1 embodiment and comparative example
Although present invention has been description to a certain degree, significantly, under the condition not departing from the spirit and scope of the present invention, can carry out the suitable change of each condition.Be appreciated that and the invention is not restricted to described embodiment, and be attributed to the scope of claim, it comprises the equivalent replacement of described each factor.
Claims (10)
1. an aromatization of methanol catalyst, described catalyst comprises:
(1) H-ZSM-5 molecular sieve mixture, described H-ZSM-5 molecular sieve mixture comprise silica alumina ratio be 18 ~ 75 H-ZSM-5 first molecular sieve and silica alumina ratio be 76 ~ 300 H-ZSM-5 second molecular sieve, and the mass ratio of described H-ZSM-5 first molecular sieve and described H-ZSM-5 second molecular sieve is 1:0.02 ~ 1; With
(2) the metal-modified element of described H-ZSM-5 molecular sieve mixture is carried on, described metal-modified element comprises the first metal-modified element and the second metal-modified element, wherein, described first metal-modified element is selected from Zn and Ga, described second metal-modified element is selected from Ag, La, Cu, Ce, Mg, Cd, Fe and Mo, and wherein, in metallic element quality, the quality sum of described first metal-modified element and described second metal-modified element is 0.1 ~ 8% of described H-ZSM-5 molecular sieve mixture quality, the amount of substance of described first metal-modified element and described second metal-modified element is than being 1:0.1 ~ 1.
2. catalyst according to claim 1, wherein, the silica alumina ratio of described H-ZSM-5 first molecular sieve is 25 ~ 65, is preferably 25 ~ 45;
Preferably, the silica alumina ratio of described H-ZSM-5 second molecular sieve is 80 ~ 100.
3. catalyst according to claim 1 and 2, wherein, in metallic element quality, the quality sum of described first metal-modified element and described second metal-modified element is 0.2 ~ 5% of described H-ZSM-5 molecular sieve mixture quality, is preferably 2 ~ 3%;
Preferably, the amount of substance of described first metal-modified element and described second metal-modified element is than being 1:0.2 ~ 0.6.
4. the method for the catalyst of preparation according to any one of claims 1 to 3, said method comprising the steps of:
(1) by H-ZSM-5 first molecular sieve and the mixing of H-ZSM-5 second molecular sieve, thus obtained H-ZSM-5 molecular sieve mixture;
(2) in described H-ZSM-5 molecular sieve mixture, add metal-modified elemental precursors solution, be uniformly mixed, at 60 ~ 100 DEG C, leave standstill process; Wherein, described metal-modified elemental precursors solution comprises the first metal-modified elemental precursors and the second metal-modified elemental precursors, described first metal-modified elemental precursors is selected from nitrate or the sulfate of Zn and Ga, and described second metal-modified elemental precursors is selected from nitrate or the sulfate of Ag, La, Cu, Ce, Mg, Cd, Fe and Mo; With
(3) product that obtains in step (2) is dry, grinding and roasting, thus obtained aromatization of methanol catalyst.
5. preparation method according to claim 4, wherein, described first metal-modified elemental precursors is nitrate or the sulfate of Zn, described second metal-modified elemental precursors is selected from nitrate or the sulfate of Ag, Cu and Cd, and also comprise ammonia in described metal-modified elemental precursors solution, the ratio of described first metal-modified element and the described amount of substance sum of the second metal-modified element and the amount of substance of ammonia is 1:6 ~ 1:16, is preferably 1:9 ~ 1:12.
6. preparation method according to claim 5, wherein, described metal-modified elemental precursors solution is prepared by method by comprising the following steps: (a) prepares the aqueous solution of described first metal-modified elemental precursors and described second metal-modified elemental precursors; (b) in the described aqueous solution, add ammoniacal liquor, and stir 0.5 ~ 2 hour at 25 ~ 40 DEG C.
7. the preparation method according to any one of claim 4 to 6, wherein, is uniformly mixed described in step (2) and carries out at 25 ~ 40 DEG C;
Preferably, the time be uniformly mixed is 0.5 ~ 5 hour.
8. the preparation method according to any one of claim 4 to 7, wherein, the temperature leaving standstill process described in step (2) is 60 ~ 100 DEG C, is preferably 70 ~ 90 DEG C;
Preferably, the time of described standing process is 4 ~ 48 hours, is preferably 2-24 hour, is more preferably 6 ~ 24 hours.
9. the preparation method according to any one of claim 4 to 8, wherein, described in step (3), the temperature of roasting is 500 ~ 550 DEG C.
10. the application in benzene, toluene and dimethylbenzene prepared by the aromatization of methanol catalyst according to any one of claims 1 to 3.
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