CN105498829B - A kind of aromatization of methanol catalyst and its preparation method and application - Google Patents
A kind of aromatization of methanol catalyst and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of aromatization of methanol catalyst, the catalyst includes：(1) 5 molecular sieve mixtures of H ZSM, it is 1 that 5 molecular sieve mixtures of H ZSM, which include 5 second molecular sieves of H ZSM that 5 first molecular sieves of H ZSM that silica alumina ratio is 18~75 and silica alumina ratio are 76~300 and the mass ratio of the two,:0.02~1；(2) the metal-modified element being supported in 5 molecular sieve mixtures of H ZSM, the metal-modified element includes the first metal-modified element and the second metal-modified element, wherein, the first metal-modified element is selected from Zn and Ga, the second metal-modified element is selected from Ag, La, Cu, Ce, Mg, Cd, Fe and Mo, and wherein, in terms of metallic element quality, their quality sum is the 0.1~8% of the 5 molecular sieve mixture quality of H ZSM, and the amount ratio of the substance of the two is 1:0.1~1.Preparation method the invention further relates to above-mentioned aromatization of methanol catalyst and its application in benzene, toluene and dimethylbenzene is prepared.
Description
Technical field
The present invention relates to a kind of aromatization of methanol catalyst for being used to prepare aromatic hydrocarbons and its preparation method and application and tools
Body it is related to a kind of preparing aromatization of methanol catalyst of benzene, toluene or dimethylbenzene and its preparation method and application for methanol.
Background technology
Benzene,toluene,xylene (BTX) in aromatic hydrocarbons is the important base stock of petrochemical industry, is widely used in the energy, hands over
The various fields such as logical, material, pesticide, daily use chemicals.The aromatic hydrocarbons in China is mainly taken out by oil catalytic reforming and pyrolysis gasoline hydrogenation
It carries etc. prepared by techniques, depends critically upon petroleum resources.With China's oil resource scarcity and external dependence degree it is further
It improves, the limitation of traditional aromatics production technique highlights, a kind of independent of fossil resources, new aromatic hydrocarbons there is an urgent need to seek
Production technology.It is extensive to cause people for methanol aromatic hydrocarbons (Methanol to Aromatics, referred to as " MTA ") technology as a result,
Concern becomes one of hot spot of countries in the world researcher research.
Methanol aromatic hydrocarbons is generally referred to using methanol as raw material, under the catalytic action of catalyst, carries out a series of reaction,
Prepare the aromatic hydrocarbons based on benzene, toluene and dimethylbenzene (BTX).Methanol aromatic hydrocarbons technology is from methanol hydrocarbon (Methanol to
Hydrocarbons, referred to as " MTH ") technology develops.Researcher has been devoted to improve methanol aromatics process
The yield of aromatics yield, particularly BTX, wherein it is the key that realize above-mentioned purpose and difficulty to develop the MTA catalyst haveing excellent performance
One of point.
ZSM-5 molecular sieve belongs to rhombic system, has the duct that intersects of size uniform, and one kind is ellipsoidal cross section
Straight tube shape duct (pore size be 0.54nm × 0.56nm), another kind is approximately circular Z-shaped duct (duct for section
Size is 0.52nm × 0.58nm).
Existing result of study shows Hydrogen ZSM-5 molecular sieve (H-ZSM-5 molecular sieves) catalyst due to its unique hole
Structure and acidic character are one of the most effective of MTA reactions and the catalyst mainly studied.However, traditional H-ZSM-5 molecules
The MTA performances of sieve are difficult to meet industrial requirement.At present, Mo2C、Ga2O3, the metallic elements such as Zn, Cu, Ag are normally used for being modified
H-ZSM-5 molecular sieves, to improve the aromatization of methanol performance of catalyst.The introducing of these metallic elements can not only change point
The acidity of sub- sieve catalyst can also change the specific surface area and pore structure of molecular sieve catalyst, and then influence H-ZSM-5 molecules
The MTA catalytic performances of sieve catalyst.For example, Wang Jinying etc. is modified the Zn/ZSM-5 catalyst performance prepared using excessive infusion process
Go out to be better than the Aromatization Activity of unmodified catalyst, wherein 0.5% Zn load capacity can improve 5% (chemistry of fuel of aromatics yield
Journal, 2009,37 (5)：607-612).In addition, the Ag/ZSM-5 catalyst of the preparations such as field great waves equally shows excellent aromatization
Change reactivity worth, the aromatics yield under conditions of 475 DEG C and reaction velocity is 300mL/g/h be up to 64% (chemical industry is in progress,
2010,29:470-473).But the demand that the aromatics yield of existing MTA catalyst and the stability of catalyst etc. are still improved
And space.
Invention content
Therefore, it is an object of the present invention to provide a kind of aromatization of methanol catalyst and preparation method thereof, the catalyst
There is high aromatics yield, particularly high benzene, toluene and dimethylbenzene (are referred to as " BTX ") yield.The present invention's is another
One purpose is to provide application of the aromatization of methanol catalyst in benzene, toluene and dimethylbenzene is prepared.
The purpose of the present invention is what is be achieved through the following technical solutions.
On the one hand, the present invention provides a kind of aromatization of methanol catalyst, the catalyst includes：
(1) H-ZSM-5 molecular sieve mixtures, the H-ZSM-5 molecular sieve mixtures include the H- that silica alumina ratio is 18~75
The first molecular sieves of ZSM-5 and the first molecular sieve of the second molecular sieves of H-ZSM-5 and the H-ZSM-5 that silica alumina ratio is 76~300
Mass ratio with second molecular sieves of H-ZSM-5 is 1:0.02~1；With
(2) it is carried on the metal-modified element of the H-ZSM-5 molecular sieve mixtures, the metal-modified element includes the
One metal-modified element and the second metal-modified element, wherein, the first metal-modified element be 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 terms of metallic element quality, first gold medal
The quality sum for belonging to modifying element and the second metal-modified element is the 0.1 of the H-ZSM-5 molecular sieve mixtures quality
~8%, the amount ratio of the substance of the first metal-modified element and the second metal-modified element is 1:0.1~1.
In the present invention, the metal-modified element is usually carried on the H-ZSM-5 molecular sieves in the form of the oxide
Mixture.
As used herein, term " silica alumina ratio " refers to the molar ratio of silica and aluminium oxide in molecular sieve, leads to
SiO can be often expressed as2/Al2O3。
In the present invention, the ZSM-5 molecular sieve with different silica alumina ratios can be made by conventional preparation side, for example, the
Those described in No. 13/502,607 U.S. Patent application.Then, it is exchanged by acid and H-ZSM-5 is made in ZSM-5 molecular sieve
Molecular sieve.
According to catalyst provided by the invention, wherein, the silica alumina ratios of first molecular sieves of H-ZSM-5 is preferably 25~
65, more preferably 25~45.
According to catalyst provided by the invention, wherein, the silica alumina ratios of second molecular sieves of H-ZSM-5 is preferably 80~
100。
In some preferred embodiments, the silica alumina ratio of first molecular sieves of H-ZSM-5 is 25~45 and H-
The silica alumina ratio of the second molecular sieves of ZSM-5 is 80~100.
According to catalyst provided by the invention, wherein, in terms of metallic element quality, the first metal-modified element and institute
State the quality sum of the second metal-modified element for the H-ZSM-5 molecular sieve mixtures quality 0.2~5%, preferably 2~
3%.
According to catalyst provided by the invention, wherein, the first metal-modified element and second metal-modified yuan described
The amount ratio of the substance of element is 1:0.2~0.6.
On the other hand, it the present invention provides a kind of method for preparing the catalyst, the described method comprises the following steps：
(1) the first molecular sieves of H-ZSM-5 and the second molecular sieves of H-ZSM-5 are mixed, is mixed so as to which H-ZSM-5 molecular sieves be made
Close object；
(2) metal-modified elemental precursors solution is added in into the H-ZSM-5 molecular sieve mixtures, is stirred, in 60
Stewing process at~100 DEG C；Wherein, the metal-modified elemental precursors solution includes the first metal-modified elemental precursors and second
Metal-modified elemental precursors, nitrate or sulfate of the first metal-modified elemental precursors selected from Zn and Ga, described second
Metal-modified elemental precursors are selected from the nitrate or sulfate of Ag, La, Cu, Ce, Mg, Cd, Fe and Mo；With
(3) by the reaction product obtained in step (2) drying, grinding and roasting, so that aromatization of methanol catalyst be made.
According to method provided by the invention, wherein, the first metal-modified elemental precursors are the nitrate or sulfuric acid of Zn
Salt, nitrate or sulfate and the metal-modified element of the second metal-modified elemental precursors selected from Ag, Cu and Cd
Also comprising ammonia in precursor solution, the sum of amount of substance of the first metal-modified element and the second metal-modified element with
The ratio of the amount of the substance of ammonia is 1:6~1:16, preferably 1:9~1:12.
According to method provided by the invention, wherein, the ammonia in the metal-modified elemental precursors solution is the shape with ammonium hydroxide
What formula added in, the mass percentage concentration of the ammonium hydroxide is 5~25%, preferably 10~18%.
According to method provided by the invention, wherein, the metal-modified elemental precursors solution is to be prepared by the following method
's：(a) aqueous solution of the described first metal-modified elemental precursors and the second metal-modified elemental precursors is prepared；(b) to
Ammonium hydroxide is added in the aqueous solution, and is stirred 0.5~2 hour at 25~40 DEG C.
According to preparation method provided by the invention, wherein, being stirred described in step (2) be at 25~40 DEG C into
Capable, it is preferable that the time being stirred is 0.5~5 hour.
According to method provided by the invention, wherein, the temperature of the stewing process described in step (2) is 60~100 DEG C, excellent
It is selected as 70~90 DEG C.
According to preparation method provided by the invention, wherein, the time of the stewing process described in step (2) is small for 4~48
When, preferably 2-24 hours, more preferably 6~24 hours.
In some preferred embodiments, the stewing process described in step (2) is included in stewing process 6 at 70~80 DEG C
~24 hours.
According to method provided by the invention, wherein, this field may be used in drying and grinding operation described in step (3)
Known conventional method.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, the present invention also provides the aromatization of methanol catalyst in benzene, toluene and dimethylbenzene is prepared
Using.
The method provided by the present invention for preparing aromatization of methanol catalyst and aromatization of methanol catalyst have but unlimited
In following advantageous effect：
(1) it is not intended to be restricted by theory, the present invention utilizes the difference of the acid intensity of the molecular sieve of different silica alumina ratios, modulation
The acid intensity of aromatization of methanol passes through the collective effect of two kinds of molecular sieves, it will be apparent that improves the Aromatization Activity of catalyst.
(2) it is not intended to be restricted by theory, the present invention forms the form of complex compound by excessive addition ammonium hydroxide and metal ion
H-ZSM-5 molecular sieves are modified, molecular sieve part desiliconization can be made under the conditions of weakly alkaline simultaneously, multi-stage porous is formed, have
The acidity of molecular sieve and the modification of pore passage structure are realized simultaneously conducive to by simple step, to improving BTX yields and stability
With obvious effect.
Specific embodiment
It is further illustrated the present invention below by specific embodiment, it should be understood, however, that, these embodiments are only
It is used for specifically describing in more detail, and is not to be construed as limiting the present invention in any form.
This part carries out general description to the material and test method that are arrived used in the embodiment of the present invention.Although
Many materials used in purpose and operating method are it is known in the art that still the present invention still makees herein to realize the present invention
It is described in detail as far as possible.It will be apparent to those skilled in the art that within a context, if not specified, material therefor of the present invention and
Operating method is well known in the art.
Embodiment 1
The present embodiment is used to illustrate aromatization of methanol catalyst and preparation method thereof.Specifically, aromatization of methanol catalyst
Preparation method include the following steps：
(1) the H-ZSM-5 molecular sieves 25g that silica alumina ratio is 25 and the H-ZSM-5 molecular sieve 5g that silica alumina ratio is 90 are weighed, is placed in
In reaction kettle, it is uniformly mixed.
(2) by the first metal-modified elemental precursors Zn (NO3)2·6H2The metal-modified elemental precursors AgNO of O and second3Dissolving
In 150ml deionized waters, 15% ammonium hydroxide 4.6ml is then added dropwise, 0.5h is stirred at room temperature, before obtaining metal-modified element
The mixed liquor of body and ammonium hydroxide；Wherein, the quality sum of Zn and Ag elements accounts for 2wt% and the Zn (NO of molecular sieve3)2And AgNO3
Substance amount ratio be 1:0.5.
(3) the metal-modified elemental precursors and the mixed liquor of ammonium hydroxide obtained step (2) are added in reaction kettle, and in room temperature
Then lower stirring 3h increases temperature to 80 DEG C, stands 24 hours.
(4) reaction product for obtaining step (3) is taken out, chilling cooling, dry at 100 DEG C, obtains dried sample
Product.
(5) the dried sample obtained step (4) is ground, goes to Muffle furnace internal program and is warming up to 550 DEG C of roastings
4h is made aromatization of methanol catalyst, is denoted as MTA catalyst 1.
Embodiment 2
The present embodiment is used to illustrate aromatization of methanol catalyst and preparation method thereof.Specifically, aromatization of methanol catalyst
Preparation method include the following steps：
(1) the H-ZSM-5 molecular sieves 26g that silica alumina ratio is 37 and the H-ZSM-5 molecular sieve 4g that silica alumina ratio is 80 are weighed, is placed in
In reaction kettle, it is uniformly mixed.
(2) by the first metal-modified elemental precursors Zn (NO3)2·6H2The metal-modified elemental precursors La (NO of O and second3)3·
6H2O is dissolved in 150ml deionized waters, and 0.5h is stirred at room temperature, and obtains metal-modified elemental precursors mixed liquor；Wherein, Zn
3.0wt% and the Zn (NO of molecular sieve are accounted for the quality sum of La elements3)2With La (NO3)3Substance amount ratio be 1:
0.3。
(3) the metal-modified elemental precursors solution for obtaining step (2) is added in reaction kettle, and 2h is stirred at room temperature,
Then raising temperature stands 24 hours to 90 DEG C.
(4) reaction product for obtaining step (3) is taken out, chilling cooling, dry at 100 DEG C, obtains dried sample
Product.
(5) the dried sample obtained step (4) is ground, goes to Muffle furnace internal program and is warming up to 550 DEG C of roastings
4h is made aromatization of methanol catalyst, is denoted as MTA catalyst 2.
Embodiment 3
The present embodiment is used to illustrate aromatization of methanol catalyst and preparation method thereof.Specifically, aromatization of methanol catalyst
Preparation method include the following steps：
(1) the H-ZSM-5 molecular sieves 20g that silica alumina ratio is 37 and the H-ZSM-5 molecular sieve 10g that silica alumina ratio is 80 are weighed, is put
In reaction kettle, it is uniformly mixed.
(2) by the first metal-modified elemental precursors Ga2(SO4)3·16H2The metal-modified elemental precursors Ce of O and second
(NO3)3·6H2O is dissolved in 150ml deionized waters, and 0.5h is stirred at room temperature, and obtains metal-modified elemental precursors mixed liquor；
Wherein, the quality sum of Ga and Ce elements accounts for the 2.5wt% and Ga of molecular sieve2(SO4)3With Ce (NO3)3Substance amount ratio
Example is 1:0.4 (i.e. the amount ratio of the substance of Ga elements and Ce elements be 1:0.2).
(3) the metal-modified elemental precursors mixed liquor for obtaining step (2) is added in reaction kettle, and is stirred at room temperature
Then 4h increases temperature to 90 DEG C, stands 36 hours.
(4) reaction product for obtaining step (3) is taken out, chilling cooling, dry at 100 DEG C, obtains dried sample
Product.
(5) the dried sample obtained step (4) is ground, goes to Muffle furnace internal program and is warming up to 550 DEG C of roastings
4h is made aromatization of methanol catalyst, is denoted as MTA catalyst 3.
Embodiment 4
The present embodiment is used to illustrate aromatization of methanol catalyst and preparation method thereof.Specifically, aromatization of methanol catalyst
Preparation method include the following steps：
(1) the H-ZSM-5 molecular sieves 18g that silica alumina ratio is 25 and the H-ZSM-5 molecular sieve 12g that silica alumina ratio is 97 are weighed, is put
In reaction kettle, it is uniformly mixed.
(2) by the first metal-modified elemental precursors Zn (NO3)2·6H2The metal-modified elemental precursors Cd (NO of O and second3)3·
9H2O is dissolved in 150ml deionized waters, and 15% ammonium hydroxide 3.5ml is then added dropwise, 0.5h is stirred at room temperature, obtains metal and changes
The mixed liquor of property elemental precursors and ammonium hydroxide；Wherein, the quality sum of Zn and Cd elements accounts for the 2.8wt% and Zn of molecular sieve
(NO3)2With Cd (NO3)3Substance amount ratio be 1:0.3.
(3) the metal-modified elemental precursors and the mixed liquor of ammonium hydroxide obtained step (2) are added in reaction kettle, and in room temperature
Then lower stirring 3h increases temperature to 70 DEG C, stands 36 hours.
(4) reaction product for obtaining step (3) is taken out, chilling cooling, dry at 100 DEG C, obtains dried sample
Product.
(5) the dried sample obtained step (4) is ground, goes to Muffle furnace internal program and is warming up to 550 DEG C of roastings
4h is made aromatization of methanol catalyst, is denoted as MTA catalyst 4.
Embodiment 5
The present embodiment is used to illustrate aromatization of methanol catalyst and preparation method thereof.Specifically, aromatization of methanol catalyst
Preparation method include the following steps：
(1) the H-ZSM-5 molecular sieves 27g that silica alumina ratio is 45 and the H-ZSM-5 molecular sieve 3g that silica alumina ratio is 83 are weighed, is placed in
In reaction kettle, it is uniformly mixed.
(2) by the first metal-modified elemental precursors Zn (NO3)2·6H2The metal-modified elemental precursors Mg (NO of O and second3)2·
6H2O is dissolved in 150ml deionized waters, and 0.5h is then stirred at room temperature, and obtains modifying agent mixed liquor；Wherein, Zn and Mg members
The quality sum of element accounts for 2.8wt% and the Zn (NO of molecular sieve3)2With Mg (NO3)2Substance amount ratio be 1:0.4.
(3) the metal-modified elemental precursors and the mixed liquor of ammonium hydroxide obtained step (2) are added in reaction kettle, and in room temperature
Then lower stirring 5h increases temperature to 90 DEG C, stands 12 hours.
(4) reaction product for obtaining step (3) is taken out, chilling cooling, dry at 120 DEG C, obtains dried sample
Product.
(5) the dried sample obtained step (4) is ground, goes to Muffle furnace internal program and is warming up to 550 DEG C of roastings
4h is made aromatization of methanol catalyst, is denoted as MTA catalyst 5.
Embodiment 6
The present embodiment is used to illustrate aromatization of methanol catalyst and preparation method thereof.Specifically, aromatization of methanol catalyst
Preparation method include the following steps：
(1) the H-ZSM-5 molecular sieve 30g that silica alumina ratio is 25 are weighed, are placed in reaction kettle, are uniformly mixed.
(2) by the first metal-modified elemental precursors Zn (NO3)2·6H2The metal-modified elemental precursors AgNO of O and second3Dissolving
In 150ml deionized waters, 0.5h is stirred at room temperature, obtains the mixed liquor of metal-modified elemental precursors；Wherein, Zn and Ag members
The quality sum of element accounts for 2wt% and the Zn (NO of molecular sieve3)2And AgNO3Substance amount ratio be 1:0.5.
(3) mixed liquor for the metal-modified elemental precursors for obtaining step (2) is added in reaction kettle, and is stirred at room temperature
Then 3h increases temperature to 80 DEG C, stands 24 hours.
(4) reaction product for obtaining step (3) is taken out, chilling cooling, dry at 100 DEG C, obtains dried sample
Product.
(5) the dried sample obtained step (4) is ground, goes to Muffle furnace internal program and is warming up to 550 DEG C of roastings
4h is made aromatization of methanol catalyst, is denoted as MTA catalyst 6.
Comparative example 1~4
Comparative example 1~4 be respectively adopted silica alumina ratio be 25,37,83 and 90 H-ZSM-5 molecular sieves as a comparison.
Comparative example 5
(1) the H-ZSM-5 molecular sieve 30g that silica alumina ratio is 25 are weighed, are placed in reaction kettle, are uniformly mixed.
(2) by metal-modified elemental precursors Zn (NO3)2·6H2O is dissolved in 150ml deionized waters, is stirred at room temperature
0.5h obtains metal-modified elemental precursors solution；Wherein, the quality of Zn elements accounts for the 2wt% of molecular sieve quality.
(3) the metal-modified elemental precursors solution for obtaining step (2) is added in reaction kettle, and 3h is stirred at room temperature,
Then raising temperature stands 24 hours to 80 DEG C.
(4) reaction product for obtaining step (3) is taken out, chilling cooling, dry at 100 DEG C, obtains dried sample
Product.
(5) the dried sample obtained step (4) is ground, goes to Muffle furnace internal program and is warming up to 550 DEG C of roastings
Aromatization of methanol catalyst is made in 4h.
Comparative example 6
The method identical with comparative example 5 is used to be modified silica alumina ratio for 25 H-ZSM-5 molecular sieves, difference exists
In：Metal-modified elemental precursors are AgNO3。
Comparative example 7
(1) the H-ZSM-5 molecular sieve 30g that silica alumina ratio is 90 are weighed, are placed in reaction kettle, are uniformly mixed.
(2) by metal-modified elemental precursors Zn (NO3)2·6H2O is dissolved in 150ml deionized waters, is stirred at room temperature
0.5h obtains metal-modified elemental precursors solution；Wherein, the quality of Zn elements accounts for the 2wt% of molecular sieve quality.
(3) modifier solution for obtaining step (2) is added in reaction kettle, and 3h is stirred at room temperature, then raising temperature
Degree stands 24 hours to 80 DEG C.
(4) reaction product for obtaining step (3) is taken out, chilling cooling, dry at 100 DEG C, obtains dried sample
Product.
(5) the dried sample obtained step (4) is ground, goes to Muffle furnace internal program and is warming up to 550 DEG C of roastings
Aromatization of methanol catalyst is made in 4h.
Comparative example 8
The method identical with comparative example 7 is used to be modified silica alumina ratio for 90 H-ZSM-5 molecular sieves, difference exists
In：Metal-modified elemental precursors are AgNO3。
Comparative example 9
(1) the H-ZSM-5 molecular sieve 30g that silica alumina ratio is 25 are weighed, are placed in reaction kettle, are uniformly mixed.
(2) by the first metal-modified elemental precursors Zn (NO3)2·6H2The metal-modified elemental precursors AgNO of O and second3Dissolving
In 150ml deionized waters, 0.5h is stirred at room temperature, obtains the mixed liquor of metal-modified elemental precursors；Wherein, Zn and Ag members
The quality sum of element accounts for 2wt% and the Zn (NO of molecular sieve3)2And AgNO3Substance amount ratio be 1:0.5.
(3) mixed liquor for the metal-modified elemental precursors for obtaining step (2) is added in reaction kettle, and is stirred at room temperature
Then 3h increases temperature to 80 DEG C, stands 24 hours.
(4) reaction product for obtaining step (3) is taken out, and chilling cooling is filtered and is washed with deionized to neutrality,
It is dry at 100 DEG C, obtain dried sample.
(5) the dried sample obtained step (4) is ground, goes to Muffle furnace internal program and is warming up to 550 DEG C of roastings
Aromatization of methanol catalyst is made in 4h.
Comparative example 10
The method identical with comparative example 9 is used to be modified silica alumina ratio for 90 H-ZSM-5 molecular sieves, difference exists
In：Molecular sieve used is the H-ZSM-5 molecular sieves that silica alumina ratio is 90.
Embodiment 11
Embodiment 11 uses the H-ZSM-5 molecular sieves 5g that silica alumina ratio is 90 for 25 H-ZSM-5 molecular sieves 25g and silica alumina ratio
Mixture as a comparison.
Catalyst performance evaluation
Performance evaluation is carried out to the catalyst of Examples 1 to 6 and comparative example 1~11 respectively, operational overview is as follows.Every time
The loaded catalyst of evaluation is 3.0g, and using pure methanol as raw material, at 200 DEG C, pure methanol is first passed around equipped with inertia quartz
The preheater of sand carries out MTA reactions, liquid hourly space velocity (LHSV) 2h subsequently into main reactor-1, reaction temperature is 420 DEG C, system stagnation pressure
Less than 0.05MPa, the product of MTA can be divided into gas and water, oily three-phase, and product is after drainer cools down, lighter hydrocarbons (C1-C5It is various
Alkene and alkane) etc. be directly entered the gas-chromatography on-line analysis with HP-PLOT-Q columns as gas-phase product；And liquid phase then by
Cold-trap is collected, and is taken out after a certain period of time, by liquid phase separation is water phase and oil phase with separatory funnel, mainly virtue in oil phase
Hydrocarbon, using the gas-chromatography off-line analysis with DB-WAX columns；And in water phase containing unreacted methanol and a small amount of dimethyl ether (when
Methanol conversion<Contain dimethyl ether when 100%) then by carrying the gas-chromatography off-line analysis of HP-PLOT-Q columns, water phase and oil
Mutually analyzed using internal standard method.Gas and water, all products of oil are represented, reaction result finally by normalization with carbon-based mass content
It is listed in table 1.
The catalyst performance of 1 embodiment and comparative example of table
Although present invention has been a degree of descriptions, it will be apparent that, do not departing from the spirit and scope of the present invention
Under the conditions of, the appropriate variation of each condition can be carried out.It is appreciated that the present invention is not limited to the embodiment, and it is attributed to right
It is required that range, include the equivalent replacement of each factor.
Claims (21)
1. a kind of aromatization of methanol catalyst, the catalyst include：
(1) H-ZSM-5 molecular sieve mixtures, the H-ZSM-5 molecular sieve mixtures include the H-ZSM-5 that silica alumina ratio is 18~75
First molecular sieve and silica alumina ratio are 76~300 the second molecular sieves of H-ZSM-5 and the first molecular sieves of the H-ZSM-5 and institute
The mass ratio for stating the second molecular sieves of H-ZSM-5 is 1:0.02~1；With
(2) the metal-modified element of the H-ZSM-5 molecular sieve mixtures is carried on, the metal-modified element includes the first gold medal
Belong to modifying element and the second metal-modified element, wherein, the first metal-modified element for one kind in Zn and Ga or
Two kinds, the second metal-modified element is one or more in Ag, La, Cu, Ce, Mg, Cd, Fe and Mo, Yi Jiqi
In, in terms of metallic element quality, the quality sum of the first metal-modified element and the second metal-modified element is institute
State the 0.1~8% of H-ZSM-5 molecular sieve mixture quality, the first metal-modified element and second metal-modified yuan described
The amount ratio of the substance of element is 1:0.1~1；
Wherein, the catalyst is by excessive ammonia and the first metal-modified element ion and the second metal-modified element ion
Made from the complex compound of formation is modified H-ZSM-5 molecular sieve mixtures and wherein, the first metal-modified element
Ratio with the sum of the amount of substance of the described second metal-modified element and the amount of the substance of ammonia is 1:6~1:16.
2. catalyst according to claim 1, wherein, the silica alumina ratio of first molecular sieves of H-ZSM-5 is 25~65.
3. catalyst according to claim 1, wherein, the silica alumina ratio of first molecular sieves of H-ZSM-5 is 25~45.
4. catalyst according to claim 1, wherein, the silica alumina ratio of second molecular sieves of H-ZSM-5 is 80~100.
5. catalyst according to claim 3, wherein, the silica alumina ratio of second molecular sieves of H-ZSM-5 is 80~100.
6. catalyst according to any one of claim 1 to 5, wherein, in terms of metallic element quality, first metal
The quality sum of modifying element and the second metal-modified element for the H-ZSM-5 molecular sieve mixtures quality 0.2~
5%.
7. catalyst according to any one of claim 1 to 5, wherein, in terms of metallic element quality, first metal
The quality sum of modifying element and the second metal-modified element for the H-ZSM-5 molecular sieve mixtures quality 2~
3%.
8. catalyst according to any one of claim 1 to 5, wherein, the first metal-modified element and described
The amount ratio of the substance of two metal-modified elements is 1:0.2~0.6.
9. preparing the method for catalyst described in any item of the claim 1 to 8, the described method comprises the following steps：
(1) the first molecular sieves of H-ZSM-5 and the second molecular sieves of H-ZSM-5 are mixed, so as to which the mixing of H-ZSM-5 molecular sieves be made
Object；
(2) metal-modified elemental precursors solution is added in into the H-ZSM-5 molecular sieve mixtures, is stirred, in 60~100
Stewing process at DEG C；Wherein, the metal-modified elemental precursors solution includes the first metal-modified elemental precursors and the second metal
Modifying element precursor, the first metal-modified elemental precursors are one kind or more in nitrate or sulfate selected from Zn and Ga
Kind, the second metal-modified elemental precursors are in nitrate or sulfate selected from Ag, La, Cu, Ce, Mg, Cd, Fe and Mo
Also comprising ammonia in one or more and wherein described metal-modified elemental precursors solution, the first metal-modified element and
The ratio of the sum of amount of substance of the second metal-modified element and the amount of the substance of ammonia is 1:6~1:16；With
(3) by the reaction product obtained in step (2) drying, grinding and roasting, so that aromatization of methanol catalyst be made.
10. preparation method according to claim 9, wherein, the first metal-modified elemental precursors are the nitrate of Zn
Or sulfate, the second metal-modified elemental precursors are one kind or more in nitrate or sulfate selected from Ag, Cu and Cd
Kind.
11. preparation method according to claim 10, wherein, the first metal-modified element and second metal change
Property the sum of the amount of substance of element and the ratio of the amount of the substance of ammonia be 1:9~1:12.
12. preparation method according to claim 10, wherein, the metal-modified elemental precursors solution be by include with
Prepared by the method for lower step：(a) the described first metal-modified elemental precursors and the second metal-modified elemental precursors are prepared
Aqueous solution；(b) ammonium hydroxide is added in into the aqueous solution, and is stirred 0.5~2 hour at 25~40 DEG C.
13. the preparation method according to any one of claim 9 to 12, wherein, be stirred described in step (2) be
It is carried out at 25~40 DEG C.
14. the preparation method according to any one of claim 9 to 12, wherein, be stirred described in step (2) when
Between be 0.5~5 hour.
15. the preparation method according to any one of claim 9 to 12, wherein, the temperature of stewing process described in step (2)
Spend is 60~100 DEG C.
16. the preparation method according to any one of claim 9 to 12, wherein, the temperature of stewing process described in step (2)
Spend is 70~90 DEG C.
17. the preparation method according to any one of claim 9 to 12, wherein, stewing process described in step (2)
Time is 4~48 hours.
18. the preparation method according to any one of claim 9 to 12, wherein, stewing process described in step (2)
Time is 2-24 hours.
19. the preparation method according to any one of claim 9 to 12, wherein, stewing process described in step (2)
Time is 6~24 hours.
20. the preparation method according to any one of claim 9 to 12, wherein, the temperature roasted described in step (3) is
500~550 DEG C.
21. aromatization of methanol catalyst described in any item of the claim 1 to 8 answering in benzene, toluene and dimethylbenzene is prepared
With.
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| CN112058302B (en) * | 2020-10-26 | 2023-02-28 | 陕西延长石油（集团）有限责任公司 | Preparation method and application of ZSM-5 molecular sieve catalyst |
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| CN1111090C (en) * | 1999-11-19 | 2003-06-11 | 中国科学院山西煤炭化学研究所 | Dual-component modified zeolite catalyst for aromatizing reaction of hydrocarbons |
| CN101462070B (en) * | 2007-12-17 | 2013-07-31 | 亚申科技研发中心（上海）有限公司 | Modified ZSM-5 type molecular sieve catalyst and preparation method thereof |
| CN101940942B (en) * | 2010-09-01 | 2012-07-18 | 大唐国际化工技术研究院有限公司 | ZSM-5 molecular sieve catalyst for preparing propylene by conversion of methanol and preparation method thereof |
| CN103418426B (en) * | 2012-05-16 | 2016-09-07 | 中国石油化工股份有限公司 | Binder-free methanol-to-aromatichydrocarbon hydrocarbon catalyst and preparation method thereof |
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