CN106140288B - A kind of dimethyl ether directly prepares the catalyst and its preparation method and application of hexamethylbenzene - Google Patents
A kind of dimethyl ether directly prepares the catalyst and its preparation method and application of hexamethylbenzene Download PDFInfo
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Abstract
The present invention relates to the method for preparing hexamethylbenzene, the catalyst and its preparation method and application that a kind of dimethyl ether directly prepares hexamethylbenzene is related in particular to.Catalyst is organized by mass percentage to be become, and 50%-90% modified carrier molecule sieve, 5-30% active component and the ducts 1-40% with the function that methylates with aromatisation function modify auxiliary agent；The carrier molecule sieve is one or more of ZSM-5, ZSM-12, MOR, Beta, USY molecular sieve；It is described to have the active component for the function that methylates for one or more of boric acid, ammonium borate, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate；The duct modification auxiliary agent is ZnO, Ag2O、MnO2、Ga2O3、Cr2O3、NiO、Co3O4、MoO3, one or more of CuO, PdO.The advantages that present invention has advantages of nontoxic raw materials, dimethyl ether conversion rate high, and reaction temperature is low, hexamethylbenzene high income, preparation process is environmentally protective.
Description
Technical field
The present invention relates to the method for preparing hexamethylbenzene, relates in particular to a kind of dimethyl ether and directly prepare hexamethylbenzene
Catalyst and its preparation method and application.
Background technology
Hexamethylbenzene (Hexamethylbenzene, abbreviation HMB, C12H18) it is a kind of important industrial chemicals, as medicine
Equal organic synthesis intermediates have a very wide range of applications in fields such as agricultural, medicine, printing and dyeing.In the recent period it has been reported that pregnancy
Pyromellitic acid anhydride (CN103936546A), pyromellitic acid anhydride and binary can be made through catalytic gas phase oxidation decarboxylation in base benzene
Arylamine reaction generates high-temperature resistance plastice polyimides；Polyimides is best one of the high-molecular organic material of comprehensive performance,
It is widely used in the fields such as Aeronautics and Astronautics, microelectronics, nanometer, liquid crystal, seperation film, laser.Hexamethylbenzene is as polyimides material
Material important source material and intermediate, dosage are constantly expanding.
The dominating process route of production hexamethylbenzene has at present：(1) benzene and its derivative methylation method, wherein phenol and first
It is industrial common pregnancy that alcohol, which reacts hexamethylbenzene (Journal of Organic Chemistry 1963,28,585) processed,
Base benzene manufacturing process, which, which dissolves phenol, is added drop-wise in methyl alcohol on the activated alumina that temperature is 530 DEG C, and product is through anti-
Should pipe outlet is cooling collects in the receiver, product is filtered out, then hexamethylbenzene is obtained through ethyl alcohol recrystallization.(2) alkynes is cyclized
Method, as rhodium chloride catalysis 2- butine be cyclized hexamethylbenzene processed (Journal of Molecular Catalysis 1990,60,
313) 2- butine is dissolved in tetrachloroethanes by the method, and catalyst rhodium chloride is added, is stirred at reflux reaction, filtering after having reacted
Catalyst, is evaporated under reduced pressure out unreacted 2- butine and tetrachloroethanes obtains hexamethylbenzene.The preparation method of above-mentioned hexamethylbenzene is deposited
Big, of high cost in the toxicity of the raw materials such as phenol and alkynes, rhodium chloride catalyst is of high cost, hexamethylbenzene separation process complexity etc.
Problem limits the large-scale production of hexamethylbenzene to a certain extent.Therefore, exploitation green, hexamethylbenzene efficiently, economic
Synthetic method is paid close attention to by more and more scientists.
Dimethyl ether is a kind of clean fuel of function admirable and a kind of widely used industrial chemicals.Currently, by diformazan
Ether recovery energy, which lacks the factors such as respective standard, to be influenced, and serious surplus occurs in China's dimethyl ether production capacity, using dimethyl ether as raw material
The research of exploitation high added value downstream chemical product receives significant attention.Currently, preparing the technology day of aromatic hydrocarbons using dimethyl ether as raw material
Become ripe (Journal of Industrial and Engineering Chemistry 2013,19,975), but this is reacted
Product is commonly present the problems such as aromatic hydrocarbons type is complicated, and separating difficulty is big, and economic value is low in the process.On this basis, by anti-
The catalyst and technique for answering process are adjusted, and to realize to the further exhaustive methylation of existing aromatic product, promote its life
At hexamethylbenzene, not only facilitates and improve product economic value, new product solution is also provided for dimethyl ether manufacturing enterprise.
Dimethyl ether is nontoxic, low boiling point, cheap, directly conversion hexamethylbenzene processed there are production process advantages of nontoxic raw materials, it is simple for process,
The features such as product is easily separated.Currently, the also rare report of the research for directly preparing hexamethylbenzene using dimethyl ether as raw material.
Invention content
Catalyst of hexamethylbenzene and preparation method thereof is directly prepared the object of the present invention is to provide a kind of dimethyl ether and is answered
With.
To achieve the above object, the invention adopts a technical scheme as：
A kind of dimethyl ether directly produces the catalyst of hexamethylbenzene, and catalyst is organized by mass percentage to be become, 50%-90%
It is modified with aromatisation function carrier molecule sieve, active component and 1-40% duct of the 5-30% with the function that methylates
Modify auxiliary agent；
The carrier molecule sieve is one or more of ZSM-5, ZSM-12, MOR, Beta, USY molecular sieve；
It is described to have the active component for the function that methylates for boric acid, ammonium borate, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate
One or more of；
The duct modification auxiliary agent is ZnO, Ag2O、MnO2、Ga2O3、Cr2O3、NiO、Co3O4、MoO3, in CuO, PdO one
Kind is several.
It is further preferred：Catalyst is organized by mass percentage to be become, and 75%-85% has the carrier point of aromatisation function
Son sieve, 5-15% have the active component and the ducts 1-10% modification auxiliary agent for the function that methylates；
Carrier molecule sieve is one or more of ZSM-5, Beta and USY molecular sieve, described to have the work(that methylates
The active component of energy is the one or more of phosphoric acid, boric acid and ammonium dihydrogen phosphate, and the duct modification auxiliary agent is MnO2、Ga2O3、
One or more of ZnO.
The catalyst be using infusion process by carrier molecule sieve duct modify auxiliary agent soluble-salt aqueous solution in into
Row is modified, and is obtained the carrier molecule with aromatisation function and is sieved；The active component with the function that methylates then is carried on tool
There is the carrier molecule of aromatisation function to sieve, as catalyst.
A kind of dimethyl ether directly produces the preparation method of the catalyst of hexamethylbenzene, it is characterised in that：
1) it uses infusion process to be modified, by weight percentage, carrier molecule sieve is added to duct and modifies the solvable of auxiliary agent
Property saline solution in be sufficiently stirred, be then ultrasonically treated 0-2h, then place 3-12h at room temperature, in 50-200 DEG C drying, finally
It goes in Muffle furnace, roasts 0.5-24h in 300-800 DEG C, obtain catalyst intermediate I；
2) catalyst intermediate I is added into the aqueous solution of the active component with the function that methylates, is sufficiently stirred, then
1-24h is placed at room temperature, in 40-220 DEG C of drying, is turning lastly in Muffle furnace, and 3-12h is roasted in 200-600 DEG C to get urging
Agent.
Or
1) carrier molecule sieve is added into the aqueous solution of the active component with the function that methylates according to the above ratio, fully
Stirring, then 1-24h is placed at room temperature, it in 40-220 DEG C of drying, is turning lastly in Muffle furnace, 3- is roasted in 200-600 DEG C
12h, for use；
2) it uses infusion process to be modified, the carrier molecule sieve of load active component is added to duct to the solubility for modifying auxiliary agent
It is sufficiently stirred in saline solution, is then ultrasonically treated 0-2h, then place 3-12h at room temperature, in 50-200 DEG C of drying, finally turned
Into Muffle furnace, 0.5-24h is roasted in 300-800 DEG C, obtains catalyst.
The infusion process can be step dipping or step impregnation.
A kind of dimethyl ether directly produces the application of the catalyst of hexamethylbenzene, and the catalyst is directly catalyzed for dimethyl ether
Preparation takes in the reaction of hexamethylbenzene.
Specifically, catalyst is packed into fixed bed reactors, is 10-800h in dimethyl ether volume space velocity-1, reaction temperature is
150-400 DEG C, reaction pressure carries out the synthetic reaction of hexamethylbenzene under conditions of being 0.02-3MPa.
Advantage of the present invention is as follows：The present invention provide be suitable for directly converted by dimethyl ether hexamethylbenzene processed catalyst and its
Using the features such as method for preparing catalyst is simple, raw material sources are in extensive range.The hexamethylbenzene preparation method have raw material without
The features such as poison, reaction temperature are relatively low, and dimethyl ether conversion rate is high, and hexamethylbenzene separation is simple.
Specific implementation mode
Embodiment 1
Weigh 5.86g AgNO3, it is dissolved in 80mL deionized waters, is configured to silver nitrate solution.By above-mentioned silver nitrate solution
It is added in 25g Beta molecular sieves and 17.5g MOR molecular sieve mixtures, is sufficiently stirred mixing, be ultrasonically treated 1.5h, then
10h is placed at room temperature；Then it goes in baking oven, in 120 DEG C of drying；It is turning lastly in Muffle furnace, roasts 12h in 550 DEG C, must urge
Agent intermediate I.
The concentrated phosphoric acid for weighing 11.37g a concentration of 85%, is dissolved in 60mL deionized waters, is configured to phosphoric acid solution, will be above-mentioned
Phosphoric acid solution is added to aforementioned catalytic agent intermediate I, is sufficiently stirred, then places 3h at room temperature, goes in baking oven, in 130 DEG C
Drying, is turning lastly in Muffle furnace, and 6h is roasted in 400 DEG C, and to get catalyst needed for reaction, (catalyst group becomes 8%Ag2O&
7%P2O5&35%MOR&50%Beta).
Catalyst produced above is fitted into fixed bed reactors, is 400h in dimethyl ether volume space velocity-1, reaction temperature
It it is 320 DEG C, reaction pressure carries out the synthetic reaction of hexamethylbenzene under conditions of being 0.5MPa.Dimethyl ether conversion rate is 87.46%,
Hexamethylbenzene is selectively 42.38%.
Embodiment 2
Weigh 17.41g Pd (NO3)2·2H2O is dissolved in 110mL dilute nitric acid solutions, is configured to palladium nitrate solution.It will be upper
It states palladium nitrate solution to be added in 41g Beta molecular sieves, is sufficiently stirred mixing, be ultrasonically treated 1h, then place 8h at room temperature；
Then it goes in baking oven, in 150 DEG C of drying；It is turning lastly in Muffle furnace, roasts 6h in 550 DEG C, obtain catalyst intermediate I.
Weigh 8.88g H3BO3, it is dissolved in 200mL deionized waters, is configured to boric acid solution, above-mentioned boric acid solution is added
It to aforementioned catalytic agent intermediate I, is sufficiently stirred, then places 8h at room temperature, go in baking oven, in 130 DEG C of drying, be turning lastly to
In Muffle furnace, 12h is roasted in 450 DEG C, and to get catalyst needed for reaction, (catalyst group becomes 8%PdO&10%B2O3&82%
Beta)。
Catalyst produced above is fitted into fixed bed reactors, is 150h in dimethyl ether volume space velocity-1, reaction temperature
It it is 300 DEG C, reaction pressure carries out the synthetic reaction of hexamethylbenzene under conditions of being 0.8MPa.Dimethyl ether conversion rate is 93.86%,
Hexamethylbenzene is selectively 41.22%.
Embodiment 3
Weigh 36.54g Zn (NO3)2·6H2O is dissolved in 65mL deionized waters, is configured to zinc nitrate solution.By above-mentioned nitre
Sour zinc solution is added in 35g USY molecular sieve molecular sieves, is sufficiently stirred mixing, is ultrasonically treated 0.5h, then place at room temperature
10h；Then it goes in baking oven, in 130 DEG C of drying；It is turning lastly in Muffle furnace, roasts 12h in 550 DEG C, obtain catalyst intermediate
Ⅰ。
8.88g boric acid is weighed, is dissolved in 160mL deionized waters, is configured to boric acid solution, above-mentioned boric acid solution is added to
Aforementioned catalytic agent intermediate I, is sufficiently stirred, then places 6h at room temperature, goes in baking oven, in 90 DEG C of drying, is turning lastly to horse
Not in stove, 6h is roasted in 400 DEG C, and to get catalyst needed for reaction, (catalyst group becomes 20%ZnO&10%B2O3&70%USY).
Catalyst produced above is fitted into fixed bed reactors, is 400h in dimethyl ether volume space velocity-1, reaction temperature
It it is 350 DEG C, reaction pressure carries out the synthetic reaction of hexamethylbenzene under conditions of being 1.5MPa.Dimethyl ether conversion rate is 76.81%,
Hexamethylbenzene is selectively 31.52%.
Embodiment 4
Weigh 14.61g Ga (NO3)3·H2O is dissolved in 240mL deionized waters, is configured to gallium nitrate solution.By above-mentioned nitre
Sour Gallium solution is added in 37.5g modenites, is sufficiently stirred mixing, is ultrasonically treated 1.5h, then place 10h at room temperature；So
After go in baking oven, in 130 DEG C drying；It is turning lastly in Muffle furnace, roasts 18h in 500 DEG C, obtain catalyst intermediate I.
Weigh 9.13g ZnO (NO3)3·6H2O is dissolved in 90mL deionized waters, is configured to zinc nitrate solution.By above-mentioned nitre
Sour zinc solution is added in aforementioned catalytic agent intermediate I, is sufficiently stirred mixing, is ultrasonically treated 1h, then place 8h at room temperature；So
After go in baking oven, in 110 DEG C drying；It is turning lastly in Muffle furnace, roasts 15h in 500 DEG C, obtain catalyst intermediate II.
Weigh 8.10g NH4H2PO4, it is dissolved in 70mL deionized waters, is configured to ammonium dihydrogen phosphate, by above-mentioned phosphoric acid
Dihydro ammonium salt solution is added to aforementioned catalytic agent intermediate II, is sufficiently stirred, then places 22h at room temperature, goes in baking oven, in
120 DEG C of drying, are turning lastly in Muffle furnace, and 9h is roasted in 400 DEG C, and to get catalyst needed for reaction, (catalyst group becomes 10%
Ga2O3&5%ZnO&10%P2O5&75%MOR).
Catalyst produced above is fitted into fixed bed reactors, is 200h in dimethyl ether volume space velocity-1, reaction temperature
It it is 320 DEG C, reaction pressure carries out the synthetic reaction of hexamethylbenzene under conditions of being 0.5MPa.Dimethyl ether conversion rate is 91.83%,
Hexamethylbenzene is selectively 22.83%.
Embodiment 5
The manganese nitrate solution for weighing 20.58g a concentration of 50%, is dissolved in 60mL deionized waters, is configured to manganese nitrate solution.
Above-mentioned manganese nitrate solution is added in 42.5g Beta molecular sieves, mixing is sufficiently stirred, is ultrasonically treated 2h, then put at room temperature
Set 8h；Then it goes in baking oven, in 80 DEG C of drying；It is turning lastly in Muffle furnace, roasts 20h in 350 DEG C, obtain catalyst intermediate
Ⅰ。
The concentrated phosphoric acid for weighing 4.06g a concentration of 85%, is dissolved in 80mL deionized waters, is configured to phosphoric acid solution, will be above-mentioned
Phosphoric acid solution is added to aforementioned catalytic agent intermediate I, is sufficiently stirred, then places 6h at room temperature, goes in baking oven, in 120 DEG C
Drying, is turning lastly in Muffle furnace, and 8h is roasted in 400 DEG C, and to get catalyst needed for reaction, (catalyst group becomes 10%MnO2&
5%P2O5&85%Beta).
Catalyst produced above is fitted into fixed bed reactors, is 100h in dimethyl ether volume space velocity-1, reaction temperature
It it is 280 DEG C, reaction pressure carries out the synthetic reaction of hexamethylbenzene under conditions of being 0.1MPa.Dimethyl ether conversion rate is 70.81%,
Hexamethylbenzene is selectively 16.93%.
Embodiment 6
Weigh 35.37g Cu (NO3)2·3H2O is dissolved in 80mL deionized waters, is configured to copper nitrate solution.By above-mentioned nitre
Sour copper solution is added in 40g USY molecular sieves, is sufficiently stirred mixing, is ultrasonically treated 0.5h, then place 8h at room temperature；Then
It goes in baking oven, in 150 DEG C of drying；It is turning lastly in Muffle furnace, roasts 8h in 500 DEG C, obtain catalyst intermediate I.
Weigh 4.44g H3BO3, it is dissolved in the deionized water of 350mL, is configured to boric acid solution, above-mentioned boric acid solution is added
Enter to aforementioned catalytic agent intermediate I, be sufficiently stirred, then place 10h at room temperature, go in baking oven, in 120 DEG C of drying, finally
It goes in Muffle furnace, 8h is roasted in 500 DEG C, and to get catalyst needed for reaction, (catalyst group becomes 15%CuO&5%B2O3&80%
USY)。
Catalyst produced above is fitted into fixed bed reactors, is 200h in dimethyl ether volume space velocity-1, reaction temperature
It it is 330 DEG C, reaction pressure carries out the synthetic reaction of hexamethylbenzene under conditions of being 0.8MPa.Dimethyl ether conversion rate is 86.85%,
Hexamethylbenzene is selectively 34.28%.
Embodiment 7
Weigh 26.33g Cr (NO3)3·9H2O is dissolved in 60mL deionized waters, is configured to chromium nitrate solution.By above-mentioned nitre
Sour chromium solution is added in 40g Beta molecular sieves, is sufficiently stirred mixing, is ultrasonically treated 2h, then place 6h at room temperature；Then
It goes in baking oven, in 80 DEG C of drying；It is turning lastly in Muffle furnace, roasts 6h in 500 DEG C, obtain catalyst intermediate I.
The phosphoric acid for weighing 8.12g a concentration of 85%, is dissolved in 60mL deionized waters, is configured to phosphoric acid solution, by above-mentioned phosphorus
Acid solution is added to aforementioned catalytic agent intermediate I, is sufficiently stirred, then places 6h at room temperature, goes in baking oven, in 110 DEG C of bakings
It is dry, it is turning lastly in Muffle furnace, 8h is roasted in 450 DEG C, and to get catalyst needed for reaction, (catalyst group becomes 10%Cr2O3&
10%P2O5&80%Beta).
Catalyst produced above is fitted into fixed bed reactors, is 300h in dimethyl ether volume space velocity-1, reaction temperature
It it is 325 DEG C, reaction pressure carries out the synthetic reaction of hexamethylbenzene under conditions of being 1.5MPa.Dimethyl ether conversion rate is 77.32%,
Hexamethylbenzene is selectively 17.38%.
Embodiment 8
The manganese nitrate solution for weighing 30.87g a concentration of 50%, is dissolved in 30mL deionized waters, is configured to manganese nitrate solution.
Above-mentioned manganese nitrate solution is added in 27.5g Beta molecular sieves, mixing is sufficiently stirred, is ultrasonically treated 1h, then put at room temperature
Set 9h；Then it goes in baking oven, in 110 DEG C of drying；It is turning lastly in Muffle furnace, roasts 6h in 450 DEG C, obtain catalyst intermediate
Ⅰ。
Weigh 27.71g Zn (NO3)2·6H2O is dissolved in 50mL deionized waters, is configured to zinc nitrate solution.By above-mentioned nitre
Sour zinc solution is added in aforementioned catalytic agent intermediate I, is sufficiently stirred mixing, is ultrasonically treated 1h, then place 8h at room temperature；So
After go in baking oven, in 110 DEG C drying；It is turning lastly in Muffle furnace, roasts 6h in 500 DEG C, obtain body II in catalyst.
A concentration of 85% concentrated phosphoric acids of 12.18g are weighed, is dissolved in 60mL deionized waters, is configured to phosphoric acid solution, by above-mentioned phosphorus
Acid solution is added in aforementioned catalytic agent intermediate II, is sufficiently stirred, then places 15h at room temperature, is gone in baking oven, in 150
DEG C drying, be turning lastly in Muffle furnace, in 450 DEG C roast 5h to get catalyst needed for reaction (catalyst group become 15%
MnO2&15%ZnO&15%P2O5&55%Beta molecular sieves).
Catalyst produced above is fitted into fixed bed reactors, is 100h in dimethyl ether volume space velocity-1, reaction temperature
It it is 280 DEG C, reaction pressure carries out the synthetic reaction of hexamethylbenzene under conditions of being 0.1MPa.Dimethyl ether conversion rate is 68.42%,
Hexamethylbenzene is selectively 38.53%.
Embodiment 9
The manganese nitrate solution for weighing 12.35g a concentration of 50%, is dissolved in 60mL deionized waters, is configured to manganese nitrate solution.
Above-mentioned manganese nitrate solution is added in 30g USY molecular sieves, mixing is sufficiently stirred, is ultrasonically treated 1h, then place at room temperature
6h；Then it goes in baking oven, in 110 DEG C of drying；It is turning lastly in Muffle furnace, roasts 6h in 500 DEG C, obtain catalyst intermediate I.
Weigh 14.60g Ga (NO3)3·H2O is dissolved in 60mL deionized waters, is configured to gallium nitrate solution.By above-mentioned nitre
Sour Gallium solution is added to aforementioned catalytic agent intermediate I, is sufficiently stirred mixing, is ultrasonically treated 1.5h, then place 8h at room temperature；So
After go in baking oven, in 120 DEG C drying；It is turning lastly in Muffle furnace, roasts 6h in 500 DEG C, obtain catalyst intermediate II.
Weigh 23.75g Zn (NO3)2·6H2O is dissolved in 80mL deionized waters, is configured to zinc nitrate solution.By above-mentioned nitre
Sour zinc solution is added in aforementioned catalytic agent intermediate II, is sufficiently stirred mixing, is ultrasonically treated 1h, then place 6h at room temperature；
Then it goes in baking oven, in 120 DEG C of drying；It is turning lastly in Muffle furnace, roasts 8h in 500 DEG C, obtain catalyst intermediate III.
The concentrated phosphoric acid for weighing 4.06g a concentration of 85%, is dissolved in 80mL deionized waters, is configured to phosphoric acid solution, will be above-mentioned
Phosphoric acid solution is added to aforementioned catalytic agent intermediate III, is sufficiently stirred, then places 8h at room temperature, goes in baking oven, in 110 DEG C
Drying, is turning lastly in Muffle furnace, and 6h is roasted in 500 DEG C, and to get catalyst needed for reaction, (catalyst group becomes 13%ZnO&
12%MnO2&10%Ga2O3&5%P2O5&60%USY).
Catalyst produced above is fitted into fixed bed reactors, is 100h in dimethyl ether volume space velocity-1, reaction temperature
It it is 300 DEG C, reaction pressure carries out the synthetic reaction of hexamethylbenzene under conditions of being 0.8MPa.Dimethyl ether conversion rate is 80.32%,
Hexamethylbenzene is selectively 36.73%.
Embodiment 10
The concentrated phosphoric acid for weighing 8.12g a concentration of 85%, is dissolved in 90mL deionized waters, is configured to phosphoric acid solution.It will be above-mentioned
Phosphoric acid solution is added to 12.5g HZSM-12 molecular sieves with the mixture of 27.5g Beta molecular sieves, is sufficiently stirred mixing, surpasses
Sonication 1h, then 9h is placed at room temperature；Then it goes in baking oven, in 130 DEG C of drying；It is turning lastly in Muffle furnace, in 450 DEG C
12h is roasted, catalyst intermediate I is obtained.
Weigh 9.73g Ni (NO3)2·6H2O is dissolved in 105mL deionized waters, is configured to nickel nitrate solution, by above-mentioned nitre
Sour nickel solution is added to aforementioned catalytic agent intermediate I, is sufficiently stirred, then places 10h at room temperature, goes in baking oven, in 100 DEG C
Drying, is turning lastly in Muffle furnace, roasts 12h in 400 DEG C, obtains catalyst intermediate II.
Weigh 9.06g Co (NO3)2·6H2O is dissolved in 100mL deionized waters, is configured to cobalt nitrate solution, by above-mentioned nitre
Acidic cobalt solution is added to aforementioned catalytic agent intermediate II, is sufficiently stirred, then places 6h at room temperature, goes in baking oven, in 80 DEG C
Drying, is turning lastly in Muffle furnace, and 3h is roasted in 500 DEG C, and to get catalyst needed for reaction, (catalyst group becomes 5%NiO&5%
Co3O4&10%P2O5&25%HZSM-12&55%Beta).
Catalyst produced above is fitted into fixed bed reactors, is 200h in dimethyl ether volume space velocity-1, reaction temperature
It it is 295 DEG C, reaction pressure carries out the synthetic reaction of hexamethylbenzene under conditions of being 0.3MPa.Dimethyl ether conversion rate is 68.37%,
Hexamethylbenzene is selectively 34.68%.
Embodiment 11
The tetraethyl oxyammonia solution of a concentration of 25 mass % of 1.6g NaOH, 19.52g and 208ml deionized waters are mixed
It closes uniformly, is added with stirring 28g Beta molecular sieves as crystal seed, 20g solid silicones are added after being stirred until homogeneous, it is strong to stir
Uniformly, 25 DEG C of aging 2h, then move into reaction kettle, and 40 DEG C are rapidly cooled to after 5 days in 140 DEG C of crystallization, product is centrifuged,
Washing to pH value is 8~9, and obtained solid is 10 hours dry in 100 DEG C, obtains the composite molecular screen of Beta/ZSM-5, wherein Beta
Molecular sieve accounts for 30%, and ZSM-5 molecular sieve accounts for 70%.
The manganese nitrate solution for weighing 20.58g a concentration of 50%, is dissolved in 90mL deionized waters, is configured to manganese nitrate solution.
Above-mentioned manganese nitrate solution is added in the composite molecular screen of the aforementioned Beta/ZSM-5 of 41g, is sufficiently stirred mixing, is ultrasonically treated
1h, then 10h is stood at room temperature；Then it goes in baking oven, in 110 DEG C of drying；It is turning lastly in Muffle furnace, in 400 DEG C of roastings
12h obtains catalyst intermediate I.
The concentrated phosphoric acid for weighing 6.50g a concentration of 85%, is dissolved in 100mL deionized waters, is configured to phosphoric acid solution, will be above-mentioned
Phosphoric acid solution is added to aforementioned catalytic agent intermediate I, is sufficiently stirred, then stands 6h at room temperature, goes in baking oven, in 80 DEG C of bakings
It is dry, it is turning lastly in Muffle furnace, 10h is roasted in 380 DEG C, and to get catalyst needed for reaction, (catalyst group becomes 10%MnO2&
8%P2O5&24.6%Beta&57.4%).
Catalyst produced above is fitted into fixed bed reactors, is 100h in dimethyl ether volume space velocity-1, reaction temperature
It it is 300 DEG C, reaction pressure carries out the synthetic reaction of hexamethylbenzene under conditions of being 0.1MPa.Dimethyl ether conversion rate is 85.83%,
Hexamethylbenzene is selectively 33.56%.
Embodiment 12
Weigh 10.96g Zn (NO3)2·6H2O and 5.84g Ga (NO3)3·H2O is dissolved in 200mL deionized waters, is prepared
At the mixed solution of zinc nitrate and gallium nitrate.Above-mentioned mixed solution is added in 41g Beta molecular sieves, mixing is sufficiently stirred,
It is ultrasonically treated 1.5h, then places 8h at room temperature；Then it goes in baking oven, in 110 DEG C of drying；It is turning lastly in Muffle furnace, in
500 DEG C of roasting 6h, obtain catalyst intermediate I.
The concentrated phosphoric acid for weighing 6.50g a concentration of 85%, is dissolved in 110mL deionized waters, is configured to phosphoric acid solution, will
Above-mentioned phosphoric acid solution is added to aforementioned catalytic agent intermediate I, is sufficiently stirred, then places 6h at room temperature, goes in baking oven, in
130 DEG C of drying, are turning lastly in Muffle furnace, and 8h is roasted in 450 DEG C, and to get catalyst needed for reaction, (catalyst group becomes 6%
ZnO&4%Ga2O3&8%P2O5&82%Beta).
Catalyst produced above is fitted into fixed bed reactors, is 100h in dimethyl ether volume space velocity-1, reaction temperature
It it is 285 DEG C, reaction pressure carries out the synthetic reaction of hexamethylbenzene under conditions of being 0.2MPa.Dimethyl ether conversion rate is 86.37%,
Hexamethylbenzene is selectively 26.33%.
Claims (8)
1. a kind of dimethyl ether directly produces the preparation method of the catalyst of hexamethylbenzene, it is characterised in that：
The catalyst is organized by mass percentage to be become, and there is 50%-90% carrier molecule sieve, the 5-30% of aromatisation function to have
Auxiliary agent is modified in the active component for the function that methylates and the ducts 1-40%；
The carrier molecule sieve is one or more of ZSM-5, ZSM-12, MOR, Beta, USY molecular sieve；
The presoma of the active component with the function that methylates is boric acid, ammonium borate, phosphoric acid, ammonium dihydrogen phosphate, phosphoric acid hydrogen
One or more of diammonium；
The duct modification auxiliary agent is ZnO, Ag2O、MnO2、Ga2O3、Cr2O3、NiO、Co3O4、MoO3, one kind in CuO, PdO or
It is several；
The preparation method of the catalyst is as follows：
1）It is modified using infusion process, by weight percentage, carrier molecule sieve is added to duct to the soluble-salt for modifying auxiliary agent
It is sufficiently stirred in aqueous solution, is then ultrasonically treated 0-2h, then place 3-12h at room temperature, in 50-200 DEG C of drying, be turning lastly to
In Muffle furnace, 0.5-24h is roasted in 300-800 DEG C, obtains catalyst intermediate I；
2）Catalyst intermediate I is added into the aqueous solution of the active component with the function that methylates, is sufficiently stirred, then in room
Temperature is lower to place 1-24h, in 40-220 DEG C of drying, is turning lastly in Muffle furnace, and 3-12h is roasted in 200-600 DEG C to get catalysis
Agent.
2. a kind of dimethyl ether directly produces the preparation method of the catalyst of hexamethylbenzene, it is characterised in that：
The catalyst is organized by mass percentage to be become, and there is 50%-90% carrier molecule sieve, the 5-30% of aromatisation function to have
Auxiliary agent is modified in the active component for the function that methylates and the ducts 1-40%；
The carrier molecule sieve is one or more of ZSM-5, ZSM-12, MOR, Beta, USY molecular sieve；
The presoma of the active component with the function that methylates is boric acid, ammonium borate, phosphoric acid, ammonium dihydrogen phosphate, phosphoric acid hydrogen
One or more of diammonium；
The duct modification auxiliary agent is ZnO, Ag2O、MnO2、Ga2O3、Cr2O3、NiO、Co3O4、MoO3, one kind in CuO, PdO or
It is several；
The preparation method of the catalyst is as follows：
1）By weight percentage, carrier molecule sieve is added into the aqueous solution of the active component with the function that methylates, is filled
Divide stirring, then place 1-24h at room temperature, in 40-220 DEG C of drying, be turning lastly in Muffle furnace, 3- is roasted in 200-600 DEG C
12h, for use；
2）It is modified using infusion process, the carrier molecule sieve of load active component is added to duct to the soluble brine for modifying auxiliary agent
It is sufficiently stirred in solution, is then ultrasonically treated 0-2h, then place 3-12h at room temperature, in 50-200 DEG C of drying, be turning lastly to horse
Not in stove, 0.5-24h is roasted in 300-800 DEG C, obtains catalyst.
3. dimethyl ether as described in claim 1 or 2 directly produces the preparation method of the catalyst of hexamethylbenzene, feature exists
In：The infusion process can be step dipping or step impregnation.
4. catalyst prepared by a kind of claim 1-3 any one of them preparation methods.
5. dimethyl ether as described in claim 4 directly produces the catalyst of hexamethylbenzene, it is characterised in that：Catalyst presses quality
Percentage group becomes, 75%-85% with aromatisation function carrier molecule sieve, active components of the 5-15% with the function that methylates
Auxiliary agent is modified with the ducts 1-10%；
Carrier molecule sieve is one or more of ZSM-5, Beta and USY molecular sieve, described to have the function that methylates
The presoma of active component is the one or more of phosphoric acid, boric acid and ammonium dihydrogen phosphate, and the duct modification auxiliary agent is MnO2、
Ga2O3, one or more of ZnO.
6. directly producing the catalyst of hexamethylbenzene by the dimethyl ether described in claim 4 or 5, it is characterised in that：The catalysis
Agent is to sieve carrier molecule using infusion process to be modified in the soluble-salt aqueous solution that auxiliary agent is modified in duct, and obtaining has virtue
The carrier molecule of structure function sieves；The active component with the function that methylates then is carried on the carrier with aromatisation function
On molecular sieve, as catalyst.
7. the dimethyl ether described in a kind of claim 4 directly produces the application of the catalyst of hexamethylbenzene, it is characterised in that：It is described
Catalyst is produced for dimethyl ether direct catalytic conversion in the reaction of hexamethylbenzene.
8. dimethyl ether as described in claim 7 directly produces the application of the catalyst of hexamethylbenzene, it is characterised in that：It will catalysis
Agent is packed into fixed bed reactors, is 10-800h in dimethyl ether volume space velocity-1, reaction temperature is 150-400 DEG C, and reaction pressure is
The preparation reaction of hexamethylbenzene is carried out under conditions of 0.02-3MPa.
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| CN201510158015.5A CN106140288B (en) | 2015-04-03 | 2015-04-03 | A kind of dimethyl ether directly prepares the catalyst and its preparation method and application of hexamethylbenzene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1338332A (en) * | 2000-08-11 | 2002-03-06 | 中国石油化工股份有限公司 | Catalyst for preparing dimethyl ether and its preparing process |
| CN1542094A (en) * | 2003-04-29 | 2004-11-03 | 中国石油化工股份有限公司 | Cracking catalyst containing molecular sieve and manganese |
| CN103357430A (en) * | 2012-03-30 | 2013-10-23 | 中国科学院大连化学物理研究所 | Cocrystallization molecular sieve catalyst for aromatization, as well as preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1338332A (en) * | 2000-08-11 | 2002-03-06 | 中国石油化工股份有限公司 | Catalyst for preparing dimethyl ether and its preparing process |
| CN1542094A (en) * | 2003-04-29 | 2004-11-03 | 中国石油化工股份有限公司 | Cracking catalyst containing molecular sieve and manganese |
| CN103357430A (en) * | 2012-03-30 | 2013-10-23 | 中国科学院大连化学物理研究所 | Cocrystallization molecular sieve catalyst for aromatization, as well as preparation method and application thereof |
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